(Doi 10.1515 - 9783110614435-002) Murzin, Dmitry Yu. - Engineering Catalysis - 2. Engineering Catalysts

2 Engineering catalysts
2.1 Catalyst design
Heterogeneous catalysts, as discussed in Chapter 1, are nanomaterials and thus

their active sites should be designed on the nanometer level, which requires under-
standing of catalytic phenomena on the molecular level.
While at the reactor level bulk density (mass per unit volume of bulk catalyst,
packed density) is important, at the mesoscale level particle density (mass per unit
volume of pellet, apparent density) and true solid density (mass per unit volume of
solid) play a crucial role.
These latter parameters are related to catalyst porosity as catalytic materials
usually possess a well-developed pore structure (Fig. 2.1).
Fig. 2.1 illustrates different types of pores. Open pores, which could be intercon-
nected, transport (passing) or dead-end, are accessible while reactants cannot ac-
cess closed pores. Porosity here could be defined as the volume of pores per total
volume of the solid, including the pores. The following parameters are typically
used to characterize porosity of catalytic materials: specific surface area (total sur-
face area per mass of solid, m2 g–1), specific pore volume (total pore volume per
mass of solid, cm3 g–1), pore size (nm) and its distribution (which can be broad or
narrow, mono- or multi-modal).
For pore size the following classification, proposed by International Union of
Pure and Applied Chemistry (IUPAC) is commonly accepted (Fig. 2.2), even if it is a
bit awkward to refer to materials with a pore size of less than one nanometer (for
example, zeolites) as microporous materials.
Shaped catalysts particles (mm range) are applied industrially on a macro-
scopic level. Thus, catalysis engineering requires knowledge of catalytic materials,
their activity, stability, mechanical strength, porosity, preparation and characteriza-
tion, understanding of reaction mechanisms and kinetics, as well as catalyst deacti-
vation. Preparation and characterization of catalytic materials is described in
Chapter 2, while the principles of kinetic modeling, including a description of deac-
tivation, will be presented in Chapter 3.
In addition to intrinsic kinetics, transport phenomena and reactor engineering
constitute an essential part of catalytic engineering. This is related to the fact, that
under industrial conditions, the rates of chemical transformations are very often af-
fected by the rates of other processes, and particularly by mass transfer processes.
The main mass transfer effects in heterogeneously catalyzed processes are: internal
diffusion inside the porous catalyst particles/layers, external diffusion in the laminar
film surrounding the catalyst particles, and – in multiphase reactors – the gas-liquid
or liquid-liquid mass transfer resistance at the phase boundary. The description of
mass transfer effects and diffusion phenomena will be addressed in Chapter 3.
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50 2 Engineering catalysts
Interconnected
(open)
Ink bottle Funnel Uniform
shaped shaped size
Dead end
Passing (open)
(open) Closed
(A) (B)
Fig. 2.1: Pore structure with different types of pores. A ([1]) and B ([2]).
Micropores Mesopores Macropores
Activated carbon, Mesoporous materials Ceramics

zeolites
2 nm 50 nm
Fig. 2.2: Classification of pores.
Finally, for the understanding of the events occurring at macroscopic or reactor

level (m scale) not only microscopic understanding (nm scale – active site) is re-
quired, which is mainly the goal of chemists working in the field of heterogeneous
catalysis, but also description at the mm (shaped catalyst pellet) and micron scale.
2.1.1 Being in shape
The shaping of catalysts and supports is a key step in the catalyst preparation pro-
cedure. The shape and size of the catalyst particles should promote catalytic activ-
ity, strengthen the particle resistance to crushing and abrasion, minimize the bed
pressure drop, lessen fabrication costs and distribute dust build-up uniformly.
While small particle size increases activity by minimizing the influence of internal
and external mass transfer, bed pressure drop (Fig. 2.3) increases. Thus, there is an
apparent contradiction between the desire to have small catalyst particles (less dif-
fusional length, higher activity) and to utilize large particles displaying lower pres-
sure drop.

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2.1 Catalyst design 51
Pressure
p2 Δp = p2 – p1
A Unreacted A
p1 p2
B + C + ...
Catalyst bed
Fig. 2.3: Pressure drop in fixed-bed reactors. Courtesy of Dr. E. Toukoniitty.
There are no precise guidelines about what should be the exact value of pressure
drop. It is decided on a case-by-case basis depending on a particular process technol-
ogy. As a rule of thumb, the size of catalyst particles in fixed beds is exceeding 1–2
mm to avoid high pressure drop, even if larger particles of 10–12 mm are also applied.
In addition to the size, the shape is important affecting the bed porosity ε. Bed poros-
ity for spheres, Raschig rings and cylindrical particles vary between 0.35 and 0.4, 0.5
and 0.8 depending on the wall thickness and 0.3 and 0.35, respectively.
Thus, the best operational catalysts have a shape and size that represents an
optimum economic trade-off. The requirements of the shape (Fig. 2.4) and size are
Sphere Cloverleaf extrudate Irregular granule
Ring extrudate Pellet Cylinder extrudate
Trilobe Metal gauze Monolith
Fig. 2.4: Various catalyst shapes.

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mainly driven by the type of reactor. For reactors with fixed beds (see Chapter 3),
relatively large particles are applied (several mm) to avoid pressure drop. For mov-
ing-bed reactors, spherical particles are preferred because they allow a smooth
flow. Catalyst powders of various sizes are utilized in slurry three-phase reactors
and in fluidized bed reactors, where mechanical stress is found because of colli-
sions between catalyst particles and with the reactor walls and formation of shear
force due to cavitations at high velocities. In the case of slurry reactors, resistance
to attrition is important, the size of the particles should allow easy filtration, while
the bulk density is defined by settling requirements when easy settling is required.
For fluidized bed reactors, attrition resistance is important, as well as particle size
distribution.
Compared to other shapes, spherical particles have low manufacturing costs,
but possess relatively high-pressure drop and large diffusional length, and are not
that common. Similarly, irregular granules, which are low surface area materials,
have applications limited to just a few reactions, for example, ammonia synthesis.
Extrudates of various profiling are very common (details of extrusion will be pro-
vided in Section 2.3.7.3).
Pressure drop can be regulated by making special types of extrudates, ranging
from cylindrical to rings to cloverleaf extrudates. In the particular case of natural
gas steam reforming (Chapter 4), many types of catalysts with different shapes are
available from catalyst manufacturers. Catalysts in the forms of rings, monoliths
with several holes, wagon wheels as well as some other complex geometrical
shapes (Fig. 4.61) afford a low diffusional path in addition to low pressure drop.
The mechanical stability typically deteriorates with an increase of complexity and
decrease of the wall thickness. Extrudates with a typical aspect ratio of length to
diameter of approximately 3–6 have poorer strength compared to pellets (tablets),
as the pellets possess good mechanical strength and a regular shape. This is a
very common type of catalysts used in many hydrogenation, dehydrogenation
and oxidation reactions.
Monoliths are mainly applied when high fluid flow rates are required (off-gas
cleaning for example), as they have low pressure drop.
Low residence time and low pressure drop is a feature of low surface area metal
gauzes, which are utilized in very few specific cases, such as very exothermal oxida-
tion of ammonia to NO, when longer residence times lead to excessive temperatures
and volatilization of the active catalytic phase.
Different shapes can be ranked in the following order according to their rela-
tive pressure drop: monolith<rings<pellets<extrudates<powder. It is also notable
that for fixed-bed applications pressure drop should be high enough to allow
even flow distribution across the bed, but not too high which would then lead to
compressing and recycling costs. In some instances egg-shell type of catalysts are
industrially applied to suppress internal mass transfer limitations (Fig. 2.5).

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Uniform Egg-shell Egg-white Egg-yolk
Fig. 2.5: Various concentration profiles in catalyst particles: active phase.
Such egg-shell catalysts with larger grain sizes have the same or similar intrin-
sic activity as powders of a smaller size with a uniform distribution of the active
phase.
The choice of catalyst shapes is thus not straightforward and involves careful
considerations of hydrodynamics, heat and mass transfer limitations, potential
pressure drops, mechanical strength, thermal resistance to sintering and phase
transition, more efficient heat conductivity for strongly exo- and endothermic reac-
tions, as well as manufacturing methods and associated costs.
Moreover, negative effects of a noncatalytic phase (carriers, binders, rheology
improvers, lubricants, etc.) and solvents on catalytic behavior should be avoided.
As a rule of thumb for the same surface-to-volume ratio the manufacturing
costs are higher for complicated shapes (monoliths, wagon wheels, etc.) compared
to more simple ones (i.e., extrudated cylinders).
Catalysts development performed in academia in the laboratory scale is mainly
limited to powder catalysts with a size that ensures an absence of mass transfer lim-
itations. Catalyst testing is typically conducted in batch and flow reactors, although
the use of structured catalysts, such as monoliths, solid foams and fibers as well as
microstructured devices, is growing.
Cordierite is widely used as a support material for monoliths (2MgO × 2SiO2 ×
5Al2O3), especially where the operating temperature is below 1,200 °C. The surface
area of cordierite is low and the active metal cannot be deposited directly on the
monolith. Therefore it is first wash-coated, for example, with alumina, to increase the
surface area (Fig. 2.6A) resulting in a wash-coat thickness of 15–100 μm. Fig. 2.6B
shows a monolith block for a heavy duty vehicle that does not have any open pas-
sages between the channels.
As the thickness of the coating for squared channels is much higher than in
other parts (Fig. 2.6A), especially at the corners, other geometries are possible, al-
lowing more uniform wash-coating (Fig. 2.7).
The manufacturing of monolithic catalysts is inherently more costly than of
other shapes such as pellets or powders. The economic benefits of using monoliths
should be thus clearly demonstrated by exceeding higher catalyst costs and invest-
ments in research and development. In particular when the annual volume of each
catalyst is small, it is difficult to justify the dedicated research. In addition, cordier-
ite has some limitations in terms of durability when in contact with alkali and alka-
line-earth above 700 °C.

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Alumina
Silica
Carbon
(A) (B)
Fig. 2.6: Monoliths: (A) wash-coating principle and (B) a monolithic block for exhaust gas
abatement from heavy duty vehicles.
Fig. 2.7: Geometry of channels in monoliths.
Fig. 2.8 shows one of the operation modes of the liquid-phase applications, the
use of cordierite is limited to a pH range of roughly pH 4–9.
Other types of structured materials have been recently suggested for use as cat-
alysts for mainly academic purposes. Some of them are also produced commercially
and are used in few specific applications related to catalysts.
Similar to monoliths, catalytic foams (Fig. 2.9) require wash-coating, as the sur-
face area of the foams made of α-alumina with several additives is just few m2 g–1.
Foams, although less mechanically stable than metal or cordierite monoliths, have
at the same time several advantages. The pressure drop can be compared to packed
beds with a similar flow pattern. Because of the template preparation method (which
will be covered in Section 2.3) a desired shape can be produced to fit the reactor size.
Wash-coating is also required for spinning disk reactors, where the two disks are
co- or counter-rotating, with each at a different rotational speed (Fig. 2.10). Although
efficient mixing and heat transfer can be achieved in such reactors, advantages of
using them for heterogeneous catalytic reactions are yet to be demonstrated.
As a final example of different catalyst shapes, it is worth mentioning fiber cat-
alysts with polyethylene as a base material further modified by grafting different
functional groups (pyridine, amines, carboxylic and sulfonic acid, or combination

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Impeller
Monoliths
(A) (B) Sampling valve
Fig. 2.8: A screw impeller reactor housing 12 pieces of structures catalysts. (A) Monolithic blocks
(left) and a corrugated metallic monolith (right). (B) General principle of operation.
Fig. 2.9: Foam blocks, made of α-alumina, require wash-coating and a subsequent introduction of
the active catalytic phase.
of them). Such materials are produced commercially and could be used as acid
catalysts similar to ion exchange resins or can be utilized in metal scavenging. For
catalytic reactions requiring a metal function, such metals can be immobilized on
the ion exchange fiber (Fig. 2.11) with a subsequent reduction with hydrogen or a
chemical reducing agent.
The fiber based catalysts can be produced in several shapes, with the diameter
of the fiber ranging from 10 to 50 μm, ensuring a short diffusional path. The swell-
ing of such fibers in many solvents and low mechanical strength are a disadvan-
tage. This is significantly improved in some activated carbon cloth materials, which
have very high specific surface area (above 1,500 m2 g–1), are mechanically rather
strong and can be used (after deposition of the catalytic phase) in slurry and fixed-
bed reactors (Fig. 2.12).

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Spinning disks reactor

Heat transfer fluid
Products
Light reactant Heavy reactant

(gas/liquid) (gas/liquid) High gravity
High shear
Products
Fig. 2.10: Spinning disk reactor. (From [3]).
Functional
group
Metal
Functional
group
SEM micrograph of the catalyst fibers
fiber diameter = 10 μm, fiber length = 4,000 μm
Fig. 2.11: Polyethylene fiber catalyst.
(A) (B)
Fig. 2.12: Active carbon cloth. (A) General appearance. (B) Application in a fixed-bed reactor with
several layers of carbon cloths.

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2.1.2 Catalysis informatics and high-throughput experimentation
In the recent years, catalysis informatics and high-throughput experimentation

became an essential part of catalyst development [4], enabling optimization of
operating conditions and discovery of new catalyst materials. Data mining in ca-
talysis informatics should help in predicting the required catalyst composition
and structure, allowing to achieve the required catalytic performance. To this
end analysis of available data on the catalytic reactions (activity, selectivity, sta-
bility, reaction parameters) as well as surface and bulk characterization should
be done with appropriate statistical tools and physical models to integrate this
information.
Catalytic informatics is indispensable in high-throughput combinatorial studies
that generate enormous amount of data. As an example, it can be mentioned that a
catalyst with five transition-metal components can give over 150 million possible
compositions.
On top of that not only the elemental composition should be considered but
other parameters as well, such as the precursor type, preparation (impregnation,
deposition, ion exchange, etc.) and post-treatment methods (calcination, reduc-
tion), catalyst shape and reaction parameters to name a few [5].
High-throughput experimentations in heterogeneous catalysis involve high-
throughput synthesis, characterization and screening techniques using robotics
and special software.
High-throughput qualitative or semiquantitative primary screening focused on
discovery is typically performed on small samples and can be often done in uncon-
ventional reactors. During primary screening, both false positives and especially
false negatives should be minimized. Evolutionary strategies in high-throughput
development of heterogeneous catalysts are based on creating new catalysts from
the best catalysts of the previous generation by qualitative (replacing one or more
chemical elements by others) and quantitative mutations (changing concentration
of one or more compounds), as well as crossover (exchanging components of two
materials of the previous generation). Selection of the best catalysts is based on the
position of catalysts according to ranking.
For primary screening, one of the applied options is preparation of solid cata-
lysts as thin-film spots on the surface of wafer substrates allowing deposition of
hundreds to thousands of small spots of differently composed materials on a sup-
port. Such approach involves a limited number of preparation steps without, how-
ever, a guarantee that the catalysts would have the same structure as bulk
catalysts because of small amounts and potential interactions with the support.
Obviously, hydrodynamics as well as mass and heat transfer are different from
lab-scale reactors.
An interesting option in the high-throughput catalysis is to use single pellets
that might, but not necessarily, behave like pellets in an industrial catalyst bed.

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The next level is secondary screening when the so-called primary “hits” are
confirmed and optimized using reactors, catalyst shapes and analytics resembling
real-life applications.
Table 2.1 gives a comparison between these stages of screening.
Tab. 2.1: Comparison between stages 1 and 2 in combinatorial screening (modified from [6]).
Stage  Stage 
Throughput Very high (up to , experiments Moderate (up to  experiments per day)
per day)
Synthesis Methods from inorganic chemistry, Methods similar to industrial preparation,

small amounts (micrograms) large amounts (.– g)
Testing Fast testing, conditions different from Lab reactors, considerations of

lab reactors hydrodynamics, heat and mass transfer
Analytics Dedicated, qualitative and Quantitative (conversion, selectivity),

semiquantitative generic
Application Discovery of novel materials Improvement of known systems,

investigation of the influence of
promoters, kinetics and deactivation
Conventional fixed-bed microreactors with complete analysis of reactants and prod-

ucts and evaluation of the mass balance closure can be used in the tertiary screen-
ing phase. Alternatively, piloting can proceed directly from secondary screening.
Preparation of industrial catalysts involves shaping to obtain granulates, beads
or pellets as will be discussed later. Such parallel shaping of catalyst powders would
be desirable on commercial synthesis platforms not yet being available. Industrial
preparation should be also robust, easy to operate and control, cost-efficient in terms
of precursors and ecologically friendly avoiding toxic and harmful waste.
Machine learning can assist high-throughput screening efforts by finding corre-
lations between structure and performance [7]. For analysis of macroscopic cataly-
sis data, partial least squares, principal component analysis and artificial neural
networks (ANN) are used [8, 9]. These and other statistical classification and regres-
sion models help in extracting information from the experimental data, being lim-
ited in their ability to generalize beyond the input data. For ANN, the training set
must be representative of the test set. After a proper training, in the subsequent ex-
ecution phase the ANN is fed with new cases providing an output, which should be
properly validated.
A particular challenge in heterogeneous catalysis is finding adequate descriptors
because many parameters in catalyst preparation (cluster size, phases, synthesis

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2.2 Toolbox in catalysis 59
conditions, pre- and post-treatment, etc.) can influence activity, selectivity and stabil-
ity beyond just chemical composition.
Quantum chemical modeling can be utilized to generate larger datasets than in
experiments and complement experimental data, followed by training machine
learning models.
Each catalyst comprising a dataset of different catalysts is described based on
the important physicochemical properties (electronic structures, physical and
atomic properties) defining each material. Thereafter, machine learning tools can
be used to find proper descriptors for stability, activity and selectivity.
More details on the theoretical background and quantum chemical calcula-
tions in catalysis will be given in Section 2.2.17. Here, it can be mentioned that
the energy of the d-band center with respect to the Fermi level is an often used
descriptor, as it is connected to the interactions between adsorbate valence states
and the d-states of a transition metal surface. Thus, after correlating the band
center with adsorption energies, the next step is to relate the adsorption energy
of the relevant reactants with catalyst activity through linear scaling relations.
Computation of the d-band center typically requires quantum mechanical (QM)
calculations at the DFT (density functional theory) level.
QM calculations are computationally expensive, thus being limited to small cat-
alytic systems. Development of interatomic potentials (i.e., mathematical functions
for computing the potential energy of a system of atoms) with machine learning
after training with data generated by QM can substantially accelerate simulations,
keeping accuracy comparable with QM methods. Figure 2.13 describes a workflow
in catalyst design involving machine learning.
As a conclusion, machine learning combined with computational modeling and
experiments is an emerging path in knowledge-based development of heteroge-
neous catalysts.
2.2 Toolbox in catalysis
2.2.1 General overview of the characterization methods
Catalyst characterization is required for understanding relationships among physi-

cal, chemical and catalytic properties, i.e., relating catalyst structure and function,
as well as elucidating catalysts deactivation, designing procedures for regeneration
and choosing catalyst properties to minimize such deactivation. Characterization
includes the determination of physical properties such as pore size, surface area,
particle strength and morphology of the carrier and location of active species within
the carrier, elemental and molecular surface composition, elucidation of the nature
of adsorbed species, active phase – support and adsorbate – adsorbate interactions,
to name a few. Monitoring changes in the physical and chemical properties of the

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Ab initio Data
𝜕
iħ—Ψ = ĤΨ
𝜕t
Machine-learned Catalyst synthesis

potential
Potential
functions
Catalyst design
Catalyst structure Catalyst prediction

Less
Active
Active
Mechanism Microkinetic
simulation
N
j M i
ri=∑⟮kj V i ∏Ck VK⟯
j=1 k=1
Fig. 2.13: Approaches to catalyst design involving machine learning (Reproduced with permission
from [10]).
catalyst during preparation, activation and reaction stages is important for proper-
ties control. Each tool has advantages and limitations and several tools are typically
needed to provide complimentary data.
In order to get information about the structure surface species various vibrational
spectroscopies, such as infrared (IR) spectroscopy, can be applied, which although
being of low sensitivity, can be arranged in situ. High-resolution electron energy loss
spectroscopy (HREELS), Raman and sum frequency generation (SFG) are among the
other methods used. Electron spectroscopy of chemical analysis or X-ray photoelec-
tron spectroscopy (XPS) and Auger spectroscopy is mainly applied to the study of the
surfaces, but can also give information about the adsorbed species.
IR spectroscopy is used also to study the nature of surfaces, either measuring
the spectra of solid compounds directly (for example, investigating acidic OH
groups) or by utilizing probe molecules, for which important information about the

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number of acid sites and their type (Lewis, Brønsted) can be obtained. Electron mi-
croscopy in various forms, XPS, and EXAFS (extended X-ray fine structure), are
among methods widely employed to characterize surface structures (Fig. 2.14),
while X-ray diffraction is a part of the characterization toolbox aimed at studying
the bulk of the material.
IR photons X-rays
IR spectroscopy X-ray diffraction
IR photons X-rays
Catalyst
Electrons Electrons
SEM/TEM XPS
Electrons X-rays
Fig. 2.14: Input–output structures of some analytical methods.
In electron microscopy the overall contrast is caused by the different adsorption of

photons or diffraction phenomena. Transmission electron microscopy (TEM, Fig. 2.14)
is suitable for the examination of supported particles in the range down to few nano-
meters. Scanning electron microscopy (SEM) provides topographical images formed
from backscattered primary or low energy secondary electrons. An energy dispersive
X-ray spectroscopy is often attached to an SEM instrument. Electron spectroscopy of
chemical analysis (ESCA) or photoelectron spectroscopy (XPS) is a surface sensitive
technique, with the depth of the sample being in the range of – two to 10 atom layers.
Surface science methods like XPS require an ultra-high vacuum, creating what
is often called a pressure gap. Such conditions of high vacuum are necessary, as
they provide a clear path for the emitted electrons (or other particles) and prevent
collisions between the electrons and gas molecules. The average distance molecules
travel between collisions is inversely proportional to pressure.
More detailed information about EXAFS, nuclear magnetic resonance (NMR),
electron spin resonance (ESR) and Mössbauer spectroscopy will be provided in the
corresponding sections.
As this textbook is written for chemical engineers, the description of the
methods is uneven, in some instances being very basic and focusing more on the
application and interpretation side of the methods, rather than on the detailed
physics behind them. The limitations of the methods are specifically addressed,
as this information is of real importance for chemical engineers, who are not typi-
cally experts in physical methods of catalyst characterization.
Finally, a few words about classical elemental analysis. A catalyst is dissolved
in strong acids under (for example) microwave heating, followed by analysis with

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inductive coupled plasma-MS (ICP-MS, when a sample solution is introduced into

the core of inductively coupled argon plasma, which generates temperature of ap-
proximately 8,000 °C) or atomic absorption spectroscopy (AAS). In this way, essen-
tial information about the catalyst bulk composition can be obtained as it is not
related directly to surface properties of the catalyst.
One example from my industrial experience is worth mentioning in the context of elemental anal-
ysis. Once, when making such analysis of a dehydrogenation catalyst for an industrial client, a
high sulfur content was unexpectedly observed. It turned out that the purchase department of
that company (without informing the plant operator) acquired a large quantity of cheap coal-
derived benzene, instead of the usual petroleum-based one. As a consequence, sulfur was able
to penetrate through two upstream reactors (one of them with another catalyst), finally resting on
the dehydrogenation catalyst. Small savings in the feedstock price resulted in large spending for
the catalysts, which had to be replaced earlier than scheduled because of deactivation.
2.2.2 Adsorption methods
Adsorption methods provide information about the total surface area of the catalyst
and porosity (by physisorption measurements) and the number, type and nature of
adsorbed species (by chemisorption). Temperature-programmed methods (such as
desorption) are also extremely useful, for example, in investigating heterogeneity of
surfaces. Chemisorption and thermodesorption methods can be combined with
microcalorimetric measurements, providing information about heat of adsorption,
acidity distribution, surface heterogeneity and lateral interactions between adsorbed
species.
Either static or dynamic methods could be applied in studying adsorption. In
static methods adsorption is performed gravimetrically or volumetrically. The volu-
metric method uses two chambers, one a dosing section, while a sample is located
in the other one. The precision of the analysis depends on the accurate determina-
tion of the volumes, including the dead space in the sample chamber, careful tem-
perature and pressure measurements. In gravimetric measurements there is no
need for such precise calibration of volumes, as the quantity of adsorbed gas is
measured directly using a microbalance.
Dynamic methods can be arranged in single flow or pulse flow modes. The first
option relies on a flow of a gas containing the molecules to be adsorbed through a
catalytic bed. Although no vacuum system is required, making the method easy to
use, the single flow method is used much less than the pulse technique because of
the possibility of slow adsorption and a need to employ pure gases. In the pulse tech-
nique there is a sequence of pulses going through the sample until no further adsorp-
tion is seen. The amount of adsorbed molecules, which should be rather strongly
bound to the surface, is determined by summation of the gases adsorbed in all pulses.

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2.2.3 Physisorption methods
Low-temperature adsorption at a gas condensation temperature (i.e., for nitrogen

this temperature is 77 K) is generally accepted as a standard procedure for the deter-
mination of surface areas and pore size distributions of a wide range of porous ma-
terials. Physisorption measurements performed at a constant temperature allow the
determination of an adsorption isotherm, whose features provide important infor-
mation about the porous solid. The theory of nitrogen adsorption that was devel-
oped in the late 1930s by Brunauer, Emmett and Teller (thus the well-known name
of the BET method and BET theory) has substantial shortcoming because of the as-
sumptions involved. Moreover, it does not include capillary condensation in the
pores in the mathematical treatment, leading to large deviations between experi-
mental data and model predictions at higher values of relative pressures. With clear
understanding of all the flaws of the BET theory, the BET method is still very widely
used throughout the world to calculate the monolayer capacity, although some
other methods are also applied. Pore size distribution can be calculated from the
desorption branch of the isotherm. Evaporation from the mesopores is not as easy
as condensation, resulting in the differences between adsorption and desorption
branches, or in other words, hysteresis. By examining the isotherm step-by-step in
the domain of hysteresis, the mesopore volume and the mesopore size distribution
can be obtained.
The monograph by J.B. Condon [11] is an excellent source of information on var-
ious methods for measuring and calculating surface area and porosity.
2.2.3.1 Surface area determination

Surface area measurements can be performed with commercially available instru-
ments (see Fig. 2.15).
The following procedure could be applied for taking measurements (Fig. 2.15B).
The lines (V1) are filled with a known pressure of nitrogen (starting from as
low as 10–20 Torr up to 700–800 Torr). Thereafter, the valve to the flask with
the known quantity of solid material (V2) is open and the pressure (pʹ) is sta-
bilized. As plineV1 = pʹline (Vl + V2) + RTnadsorbed moles the amount of adsorbed
nitrogen can be calculated.
Different types of isotherms are obtained, depending on the type of the support
material (Fig. 2.16).
In a type I isotherm there is a monolayer adsorption on an ideal surface with sat-
uration and there are no interactions between adsorbed species. In type I, as well as
in types II and III, there is no hysteresis, showing that these materials are free from
mesopores. For a type II isotherm, multilayers starting at point B are formed. For a
type III isotherm, the incoming molecules are bound stronger to the surface when it
is gradually occupied, which is a sign of lateral interactions. Isotherm VI represents a

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High vacuum
P V1
Pressure
gauge
V2
(A) (B) Adsorbate Adsorbent
Fig. 2.15: (A) Instrument for sorption measurements (Carlo Erba Sorptometer 1900). (B) Principle
scheme of measurements.
I II III
nad
nad
nad
B
p/p0 p/p0 p/p0
IV V VI
nad
nad
nad
B
p/p0 p/p0 p/p0
Fig. 2.16: IUPAC classification of isotherms.
layer-by-layer adsorption. Types IV (the most typical for catalytic materials) and V
isotherms exhibit hysteresis in mesoporous. The formation of poly-layers and then
capillary condensation also occur during adsorption, but there are different equa-
tions governing evaporation and condensation during adsorption and desorption
(as will be explained later), thus for the same amount adsorbed there is a difference
in relative pressures observed in the gas-phase.
The hysteresis behavior could be even more complicated, as shown in Fig. 2.17A,
where the H1 type of isotherm corresponds to a narrow distribution of uniform pores,
while the H2 type reflects more complex (non-uniform) pore structures. The shape of
pores in H1 and H2 isotherms are nearly cylindrical, while slit-shaped pores with uni-
form and non-uniform sizes and shapes result in H4 and H3 isotherms, respectively.
The specific surface area can be calculated when knowing the monolayer
capacity, using the following expression:

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Type H1 Type H2 Type H3 Type H4

Adsorbed volume
Adsorbed volume
Adsorbed volume
Adsorbed volume
0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1
p/p0 p/p0 p/p0 p/p0
Fig. 2.17: Hysteresis behavior for different types of pores: adsorbed amount as a function of
relative pressure.
s = nm Am NA (2:1)
where s is the specific surface area (m2 kg−1 or typically m2 g−1), mm is the mono-
layer capacity (mol g−1), Am is the area occupied by one molecule (m2 molecule−1)
and NA is the Avogadro number equal to 6.023 × 1023 molecules mol−1. Tab. 2.2 con-
tains values of the areas occupied by common adsorbates. Typically, nitrogen is
used, however, krypton and argon adsorptions are also used, especially for low sur-
face area materials (< 1 m2 g−1).
Tab. 2.2: Values of the areas occupied by typical adsorbates.
Adsorbate Boiling point (K) Am (nm/molecule)
N . .
Ar . .
CO . .
Kr . .
In practice, the adsorbed volume is measured and the volumetric monolayer capac-
ity (recalculated for standard pressure and temperature) is reported. Thus, instead
of eq. (2.1) we get:
Vm Am NA
s= (2:2)
V
where Vm is the volumetric monolayer capacity, V is the volume of one mole at stan-
dard pressure and temperature (22.4 × 10−3 m3 mol−1).
There is, therefore, a need to calculate the value of the monolayer capacity from
experimental data for physisorption when multilayers are formed. The monolayer ca-
pacity can be calculated using the method developed by Brunauer, Emmett and

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Teller for multilayer adsorption, which was based on the approach of Langmuir, who
considered adsorption in a monolayer.
Layers of adsorbed molecules (Fig. 2.18) are divided in the first layer by the heat
of adsorption ΔHad,1 and in the second and subsequent layers by ΔHad,2 = ΔHcond’
equal to the heat of condensation.
Fig. 2.18: Schematics of desorbed layers.
Adsorption in the first layer can be described as a0PS0 = b1S1 where a0 and b1 are
adsorption coefficient on the zero layer (bare surface) and desorption coefficient
from the first layer, respectively, S0 denotes the number of empty sites available
for adsorption and S1 is the number of adsorbed molecules in the first layers.
Consequently S1 = (a0P/b1)S0 = yS0 with y = (a0P/b1). Analogously for the second
layer a1PS1 = b2S2, S2 = (a1P/b2)S1 = xyS0 with x = a1P/b2. As only adsorption in
the first layer is different: a1 = a2 = a3 = …. = an; b2 = b3 = …. = bn and subse-
quently a2PS2 = b3S3. S3 = (a2P/b3)S2 = x2yS0. For adsorption in the nth layer:
Sn = xn – 1yS0 = xn(y/x)S0 = xncS0 with c = y/x. The total amount of adsorbed mole-
P
∞ P∞ P
∞
cules is defined as nSn = ncxn S0 = cS0 nxn .
n=1 n=1 n=1
P∞
The monolayer capacity should also include the empty sites Sn = S0 +
P∞ P∞ n = 0P∞
cx S0 = S0 + cS0
n
x . Making use of infinite geometrical progression
n
nxn )
n=1 n=1 n=1
P∞
x
2 xn ) x ′ the equation for the monolayer capacity can be easily obtained:
ð1 − xÞ 1−x
n=1
x
cS0
Nads Vads ð1 − xÞ2 cx
= = = (2:3)
Nmono Vmono S + cS x ð1 − xÞð1 − x + cxÞ
0 0
1−x
As adsorption-desorption in the nth layers can be considered as liquid-vapor equi-
librium, condensation-evaporation equilibrium gives aP0 = b where P0 is the satura-
tion pressure. For adsorption of nitrogen P0 = 1 bar at 77 K. Further transformations
give x = (a/b)P = P/P0.
Linearization of eq. (2.3) results in:
1 x 1 c−1
= + x (2:4)
V 1 − x cVm cVm

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which can be presented in the graphical form (see Fig. 2.19), allowing for the calcu-
lation of the monolayer volume:
1
Vm = (2:5)
i+s
1 x
V 1–x
c –1
=s
cVm
1
= Vm
1 i+s
=i
cVm
Fig. 2.19: Linearization of BET equation.
In eq. (2.5) the slope is s = (c – 1)/cVm and the intercept is given by 1/cVm, allowing
for the calculation of the monolayer volume as the reciprocal value of the sum of
the slope and the intercept.
The linearization should be performed for the relative pressures between 0.05
and 0.3, as at higher values the deviations are becoming substantial because of var-
ious shortcomings in the model; for example, not accounting for capillary conden-
sation in the pores.
By taking the volume of the monolayer from eq. (2.2) it is possible to calculate
the specific surface area. Typically the plots for catalytic materials are presented
with the adsorbed volume calculated in cm3 g–1 at standard temperature and pres-
sure (STP). For N2 adsorption at 77 K the specific surface area (m2 g−1) is then the
monolayer volume (cm3 g−1 at STP) multiplied by coefficient 4.3532. Some typical
values for catalytic materials are given in Tab. 2.3. While reporting the surface areas
of catalytic materials one should be cautious, keeping in mind the precisions of vol-
umetric flow measurements. Reporting the values that are directly available from a
physisorption instrument, for example, 124.564 m2 g−1 does not make much sense
even if similar values appear on a regular basis in the literature. In addition, errors
in the estimation of surface areas for materials with low surface areas can be very
high, thus it is recommended that there is a sufficient amount of the sample in a
measurement unit (~40 m2).
Tab. 2.3 also contains values of the mean diameter of pores. For physisorption
of nitrogen the monolayer thickness is 0.354 nm, which means that in the case of
zeolites or activated carbon applications of BET theory, relying on an infinite

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Tab. 2.3: Typical values of surface areas for catalyst supports.
Catalyst supports Mean dp (nm) SBET (m g−)
Silica gel  

 
 
γ-AlO  
 
Zeolite .– –
Activated carbon  –,
TiO – –
Aerosil SiO – –
number of adsorbed layers is more than questionable. Even for supports like alu-
mina, a pore diameter of ~5 nm is translated in around seven layers. As the BET
method is only valid in a small pressure interval, and the physical interpretation of
it is not very easy, other less popular methods are also used for the calculation of
the monolayer capacity.
In the t-plot method, introduced by de Boer, it is assumed that in a certain iso-
therm region the micropores are already filled-up, whereas adsorption in larger pores
occurs according to some simple equation, characteristic for a large class of solids.
This equation should approximate adsorption in mesopores, macropores and on a
flat surface in a narrow pressure range just above complete filling in micropores, but
below vapor condensation in mesopores. Such an assumption may be valid, if micro-
pores are small and super-micropores are not present. Thus the thickness of the ad-
sorbed layer depends only on the relative pressure but not on the material type and
could be expressed, for example, by the equations in Fig. 2.20.
Adsorption within this pressure region, when the thickness is independent on
the material type, can be described by a simple linear dependence (Fig. 2.21).
Such linear dependence can be easily understood by expressing the thickness
of the adsorbed layer through the number of adsorbed monolayers (the ratio of the
number of adsorbed moles nad to the monolayer capacity nm) and the monolayer
thickness (0.354 nm or 3.5410−10 m for nitrogen):
nad
t= 0.354 nm (2:6)
nm
And subsequently:
nad
St = nm Am NA = 0.354 × 10 − 9 ðmÞAm NA (2:7)
t
From eq. (2.7) the number of adsorbed moles depends linearly on the thickness of the
adsorbed layer with the slope inversely proportional to the surface area of mesopores.

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1.00
0.333
Thickness of adsorbed
–5.00
t = 0.354
ln(p/p0)
layer t (nm)
Halsey
0.5
13,99
t = 0.1
0.034–log(p/p0)
Harkins–Jura–de Boer
0.00
0.00 0.50 1.00
p/p0
Fig. 2.20: Adsorbed layer thickness as a function of relative pressure.
nad
Smesopores
Fig. 2.21: Adsorbed amount as a function of

adsorbed layer thickness for a material with micro-
t and mesopores.
A dependence like the one presented in Fig. 2.21 is made through plotting an
experimentally obtained value of nad or Vad for a particular value of the relative
pressure and relating it to the thickness of the adsorbed layer for the same pressure
using correlations of t vs relative pressure.
Exercise 2.1: When nitrogen was adsorbed on a catalyst at −196 °C the following data were ob-
tained. Numerical values are given below. What is the specific surface area of the catalyst?
Calculate the pore size distribution.
Adsorption Desorption
Rel. Volume, Rel. Press, Volume, Rel. Press, Volume,

Press, adsorbed (p/p) adsorbed, (p/p) desorbed,
(p/p) (cm g−) (cm g−) (cm g−)
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .

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Adsorption Desorption
Rel. Volume, Rel. Press, Volume, Rel. Press, Volume,

Press, adsorbed (p/p) adsorbed, (p/p) desorbed,
(p/p) (cm g−) (cm g−) (cm g−)
. . . . . .

. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . .
. . . .
. .  .
500
450
400
Adsorbed volume
350
300
250
200
150
100
50
0
0.0 0.2 0.4 0.6 0.8 1.0
P/P0
Fig. E2.1. Adsorbed volume as a function of relative pressure.
For microporous materials like zeolites and active carbon with the pore size ~0.5–2
nm there are no theoretical grounds to use the BET method with the assumption of
multilayer adsorption. An ideal Langmuir equation usually overestimates the surface
area. A t-plot method could be used instead for the determination of the micropore
volume and the surface area.
For microporous materials a plot of the adsorbed volume vs the thickness of the
adsorbed layer, defined by Harkins-Jura-de Boer equation (Fig. 2.20), gives a
straight line (Fig. 2.22A). Therefore even a one point analysis at a certain value of

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W VA
t-plot
Micropore volume
1.00 1.00
(A) p/p0 t (Å)
W Micro+meso VA Slope = SA of meso

+ external surface
t-plot
Full up of micropore
Slope = total SA
1.00 1.00
(B) p/p0 t (Å)
Fig. 2.22: Application of the t-plot method for determination of micropore volume.
relative pressure is sufficient, as at this point the surface is determined by the ratio
between the volume adsorbed and the layer thickness at this particular pressure.
Fig. 2.22B provides an illustration of the t-plot method for materials containing both
micro- and mesopores.
Instead of the t-plot method for the determination of the micropore volume, a
method developed by Dubinin and his co-workers [12] could be applied. The
Dubinin–Radushkevich equation relates the volume of adsorbate and the total
volume of the micropores Vm:
" 2 #
RT p0
V = Vm exp − B ln2 (2:8)
β p
where B and β are constants and T is temperature. A linear relationship should be

found between ln V and ln2(p0/p). Although the curve is bending at low values of
log2(p0/p) extrapolation to zero gives the value of Vm.
2.2.3.2 Determination of pore size and pore size distribution

In the capillary condensation region (p/p0 > 0.4) there is capillary condensation in
the pores during both adsorption and desorption (Fig. 2.23). Evaporation from the

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Adsorption followed by Capillary evaporation

capillary condensation parallel with desorption
Fig. 2.23: Representation of pore filling during adsorption and desorption. Adsorption proceeds
through multilayer formation, while desorption is meniscus controlled.
pores is not as easy as condensation, resulting in differences between adsorption

and desorption branches (hysteresis).
In a cylindrical pore with two radii of curvature, the saturation vapor pressure
is given by the Kelvin equation:

p0 1 1 σV cos θ
ln = + (2:9)
p r1 r2 RT
where p0 is saturation pressure, σ is the surface tension of the liquid (8.72 mN m−1
for N2), V is the molar volume of liquid (N2 = 34.6 cm3 mol−1), θ is the contact angle
of the liquid with the gas (zero for liquid nitrogen). Equation (2.9) shows the result
of the interactions with the pore walls making condensation occur at a lower rela-
tive pressure than the saturation one. As the relative pressure is increased, conden-
sation occurs first in the pores of smaller radii and then progresses. The Kelvin
equation gives the possibility of estimating pore radii from a gas adsorption iso-
therm. At any equilibrium pressure p, pores of radii less than r will be filled with
condensed vapor. Application of the Kelvin equation to all points of the isotherm at
relative pressures greater than that corresponding to the monolayer volume (where
capillary condensation begins to occur) yields information concerning the volume
of gas adsorbed in pores of different radii.
Desorption occurs from hemispherical surfaces with both radii of curvature
equal to each other, thus eq. (2.9) is rearranged:
2σV cos θ
r= p +δ (2:10)
RT ln p0
The modified Kelvin equation (eq. 2.10) is the basis of Barrett, Joyner, Halenda and
Dollimore-Heal methods and contains δ which is the thickness of the adsorbed
layer and can be calculated from the Wheeler equation:
1
p0 − 3
δ = 0.734 ln ðnmÞ (2:11)
p

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Finally an expression is obtained for the estimation of the pore radii from the nitro-
gen desorption branch of isotherm:
1
0.93 p0 − 3
r = p + 0.734 ln ðnmÞ (2:12)
ln
0 p
p
The following procedure is used to calculate the pore size and pore volume distribu-
tion. The desorption branch of the experimentally measured nitrogen physisorption
is applied. Each point gives the amount adsorbed and the relative pressure. By mul-
tiplying this amount by the molar volume of liquid nitrogen (34.68 cm3 mol−1) the
pore volume is obtained. The modified Kelvin equation gives the radius at a particu-
lar value of relative pressure. The next step is to plot the volume of pores vs radius
and then calculate dV/dr at different values of r. This can be done for example, by
dividing the incremental difference in volumes (V2 – V1) by the incremental differ-
ence in corresponding radii (r2 – r1) and relating (V2 – V1)/(r2 – r1) to the average
between these two radii [(r1 + r1)/2]. A typical result is presented in Fig. 2.24.
1.2
Pore volume (cm3/g/nm)
0.9
0.6 5% Ru-10% Sn/SiO2
0.3
0
0 1 2 3 4
Pore radius (nm)
Fig. 2.24: Pore volume distribution as a function of pore radii.
Besides the suggestion that desorption proceeds from a hemispherical meniscus

while adsorption occurs on a cylindrical meniscus and thus for adsorption in
eq. (2.9) r1 = r and r2 = ∞ there are other explanations in the specialized literature,
such as changes of the contact angle caused by surface cleaning, different radii of
meniscus in adsorption and the desorption presence of interconnected pores behav-
ing differently during these processes.
For pore size distribution analysis it is not only hysteresis in nitrogen physisorp-
tion isotherm that can be used, but also mercury porosimetry. Because of the non-
wetting nature of mercury (the angle of contact of mercury with solids, θ, is above

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90° and ~140°) its intrusion into the pores is met with resistance and the pore radius
can be related to the applied pressure following the Washburn equation:
2σ cos θ
r= (2:13)
Δp
where σ is surface tension normally taken as 480 mN m−1. A comparison between

surface area determination by mercury penetration and nitrogen physisorption typi-
cally shows a discrepancy for microporous materials, which is associated with Hg
inability to penetrate small (micro)pores, uncertainty of the contact angle and sur-
face tension values and the probability of the cracking or deforming of samples.
However, mercury porosimetry remains as the most reliable method for investiga-
tion of macroporous materials.
2.2.4 Chemisorption
In addition to physisorption, which is used for the determination of specific area of

supports, the exposed surface area of the active (metal) phase and metal dispersion
can be evaluated using chemisorption. The metal dispersion D is defined as:
Ns
D= 100% (2:14)
NT
where ns is the number of surface atoms and nT is the total number of atoms.
In essence, chemisorption is the titration of surface sites by a certain adsorbate
(hydrogen, oxygen, CO), which reacts only with the active phase to form a mono-
layer. The understanding of stoichiometry (as shown in Fig. 2.25 for CO adsorption)
is important for getting the correct values of metal dispersion. In some instances,
such as the determination of Cu surface area by chemisorption with N2O, there is a
possibility of subsurface oxidation, which in pulse chemisorption (explained
below) depends on temperature (prominent above 100 °C), amount of the sample,
metal loading and the catalyst bed geometry.
O O O O O
C O C C C C C
Fig. 2.25: Different stoichiometry for CO chemisorption.
From the experimentally measured adsorbed volume the number of adsorbed moles
is calculated. Through knowing stoichiometry, the number of surface atoms is

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determined. The total number of metal atoms and subsequent metal dispersion can
be calculated by knowing metal loading.
There is a relationship between the metal dispersion and the diameter of a
metal cluster on a support that can be calculated using the following approach.
Imagine a spherical cluster of the size d. The surface of this cluster (πd2) is com-
posed of metal atoms, each with a surface corresponding to the cross section of a
particular atom SMe. Then the number of surface atoms is defined as NS = πd 2/SMe.
The total number of atoms in the cluster is proportional to the mass of the cluster
and the Avogadro number and inversely proportional to metal molecular mass:
mcluster NA Vcluster ρNA πd3 ρ NA

NT = = = (2:15)
M M 6 M
where ρ is the metal density. The metal dispersion is computed from (2.14) and
(2.15):
mcluster NA Vcluster ρNA 6M

D= = = 100% (2:16)
M M dρSMe NA
which is finally related to the diameter of metal clusters:
6M
d= 100% (2:17)
DρSMe NA
Some equations, which can be used for calculating the metal particle size (in nm)
are given here for several metals: Pt: 108/D(%); Pd: 107/D(%); Ru: 101/D(%); Ni: 97/
D(%). An assumption in these calculations is the metal surface area. If only dense
metal surfaces are considered (like 111) with smaller SMe, somewhat larger values of
metal clusters will be obtained. Because of uncertainties in the stoichiometry, the
presence of spillover, the possible formation of subsurface species and not neces-
sarily spherical cluster shape, verifying the estimation of metal particle size with
chemisorption by some other physical methods is recommended. For example, di-
ameter d can be measured or calculated from several techniques, such as high-
resolution electron microscopy, X-ray diffraction or XPS. The overall number of ad-
sorbed molecules in a monolayer could be determined by temperature-programmed
desorption, while infrared spectroscopy using a probe molecule is widely applied
for determination of the number of acid and basic sites in zeolites and mesoporous
materials. These methods will be described later in detail.
In static chemisorption methods, after a high temperature evacuation the iso-
therm is measured, followed by a subsequent low-temperature evacuation, where
physisorbed molecules are removed. In the second phase of adsorption measure-
ments only these weakly adsorbed molecules are chemisorbed back on the surface.
Subtraction of the weakly adsorbed amounts from totally adsorbed ones gives
the amount of strongly and irreversible adsorbed gas, which is then used for

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Total chemisorption
after high-T evacuation
nad (mmol g–1)
Strong chemisorption
Irreversible
Weak chemisorption
after subsequent low-T evacuation
Reversible
p (kPa)
Fig. 2.26: Principles of the back sorption method.
calculating the surface area and metal dispersion. The principles of the back sorp-
tion method are illustrated in Fig. 2.26.
Although historically the static methods for chemisorption were applied, dy-
namic methods are also often used for measuring chemisorption (Fig. 2.27A).
1.4
Cumulative volume (mL g–1 STP)
1.2
1.0
0.8
Catalyst Detector 0.6
H2, CO
0.4
0.2
0.0
–0.2
0 1 2 3 4
Pulse Response Peak number
(A) (B)
Fig. 2.27: Dynamic method for measuring chemisorption. (A) pulse-response sequence.
(B) adsorbed amounts as a function of pulse number.
Determination of the metal dispersion of a supported metal catalyst (for example,

palladium on a mesoporous support, Fig. 2.27B) could be performed by measuring
CO chemisorption. The sample should be placed into a U-tube and reduced by hy-
drogen, while increasing the temperature linearly, 5 °C min−1 to 200 °C, then main-
taining it for 2 h. After the reduction, the catalyst sample should be cooled down to
40 °C under helium flow. Chemisorption of CO is then achieved by pulsing
CO through the system and completely saturating the catalyst (Fig. 2.27B). The

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stoichiometric ratio between metal (Pd) and CO is assumed to be unity (in fact it
could depend on the cluster size, as the stoichiometry might change). The mean
particle size ds is calculated knowing the metal dispersion.
2.2.5 Temperature-programmed methods
There are several temperature-programmed techniques available for catalyst char-

acterization. A certain process (catalyst reduction, oxidation of coke, desorption of
pre-adsorbed species or their chemical reactions) is followed while the temperature
is increased linearly. This non-spectroscopic technique is inexpensive and applica-
ble to real and model catalysts.
2.2.5.1 Temperature-programmed reduction

This method is based on the reduction of a catalyst by hydrogen during temperature
ramping, while monitoring hydrogen consumption with a thermal conductivity de-
tector. Hydrogen consumption profiles are plotted as a function of temperature (or
time) as shown in Fig. 2.28.
0.09 Treated at 200 °C with NH3

prior to Pd addition
0.06
Treated at 600 °C with NH3
H2 uptake (a.u.)
0.03
Treated at 400 °C with NH3
0
–0.03
0 50 100 150 200 250 300 350 400
Temerature (°C)
Fig. 2.28: TPR of palladium supported on N-functionalized carbon nanotubes, treated with
ammonia at different temperatures prior to addition of palladium.
The number of peaks in the thermogram can be interpreted either by the presence of
different chemical species, which are reduced at different temperatures, or by the suc-
cessive reductions of one type of species. The degree of reduction or the initial oxida-
tion state (if reduction is complete) can be elucidated from the consumed amount of

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hydrogen. Finally, the positions of the peaks in temperature point the active phase
interactions with the support. Strong interactions with the support will result in a shift
in the peak maximum to higher temperatures, giving a broader peak (Fig. 2.29A).
Unsupported Supported Small nanoparticles: Large particles:

nanoparticles: nanoparticles with almost intrinsic rate TPR broadened
strong support of reduction by mass transport
interaction limitation
dM dM
dT dT
(A) T (B) T
Fig. 2.29: TPR curves. (A) Influence of support. (B) Influence of the cluster size.
In the reduction processes, where mass transport limitations are prominent, large
particles are reduced at higher temperatures and the peak is broadened (Fig. 2.29). In
the reduction processes controlled by nucleation (reduction of nickel oxides) the tem-
perature of the maximum is, conversely, increasing with a decrease in the particle
size, thus large particles are characterized by narrow and intense peaks, while small
clusters have a broader peak at higher temperatures.
As the position of the peaks may vary depending on the metal support interac-
tions, particle size and heating rate, one should be very cautious in interpreting the
thermograms and in selecting the reduction temperature from, for example, litera-
ture data, as this temperature is very sample- and condition-specific.
TPR is useful is analyzing bimetallic systems, as the number of peaks and the
shift of the peaks compared to monometallic systems provide information about the
interactions between the metals.
2.2.5.2 Temperature-programmed desorption

Temperature-programed desorption (TPD) involves heating a sample with a rising
temperature and simultaneously detecting the residual gas in the vacuum using a
mass analyzer. As the temperature rises, certain absorbed species will have enough
energy to escape and will be detected as a rise in pressure for a certain mass. A vac-
uum is needed to prevent re-adsorption, which is thus neglected in the mathemati-
cal treatment. The desorption rate goes through a maximum. At low T the coverage

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is high, but the rate constant is low and overall the desorption rate is low. As the
temperature increases the rate constant and thus desorption rate increases. At in-
termediate temperatures the desorption rate is high as both the coverage and the
rate constant are high. At higher T the coverage is virtually zero and although the
rate constant is enormous, the desorption rate is virtually zero. The temperature
of the peak maximum provides information on the binding energy of the bound
species (Fig. 2.30A) as well as decomposition path for complex organic molecules
desorption (Fig. 2.30B).
50,000
500
Mass intensities (rel. units)
40,000 400
2.
30,000 300
T (°C)
20,000 200
1.
10,000 100
4.
3.
0 0
1,500 2,000 2,500 3,000
(A) Time (s)
o-Xylene
Benzene
CH4
H2
MS signal (au)
Toluene
C2H4
C2H4
CH4
323 423 523 623 723 823 923

(B) Temperature (K)
Fig. 2.30: (A) TPD of CO from Pd/C catalysts after stearic acid decarboxylation. 1, CO; 2, hydrogen;
3, CO2; 4, methane. (B) TPD of o-xylene. (From [13].)

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Activation energy of desorption can be determined from TPD experiments at differ-

ent heating rates β = dT/dt. For the first-order desorption kinetics –dθ/dt = θke–ΔEdes /RT
with a linear heating rate T = T0 + βt the temperature dependence of the coverage is:
ΔEdes
dθ θk −
− = e RT (2:18)
dT β
which after differentiating gives:
0 1
ΔEdes ΔEdes
d2 θ k @ Edes − dθ −
− = θΔ 2 e RT + e RT A (2:19)
dT 2 β RT dT
At the peak maximum (T = Tp) it holds that – d 2θ/dT2 = 0, therefore:
dθ ΔEdes
− =θ (2:20)
dT RTp2
Elimination of the term dθ/dT and further simple manipulations give a possible de-
termination of Edes from TPD experiments with different heating rates β (Fig. 2.31).
The slope in Fig. 2.31 is equal to R/ΔEdes:
1 R T2 R kR
= ln + ln (2:21)
T ΔEdes β ΔEdes ΔEdes
2.6
2.5
103/Tp
2.4
2.3
2.2
7 8 9 10 11 12
ln(Tp2/beta)
Fig. 2.31: Determination of activation energy of first-order desorption.

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Exercise 2.2: The following TPD data were obtained with different heating rates (Fig. E2.2).
Calculate the activation energy of desorption
2.1
1.8 20°C min–1
105.5°C
1.5
15°C min–1
NH3 concentration (%)
99.5°C
1.2
10°C min–1
0.9 90.7°C
0.6 78.4°C
5°C min–1
69.9°C
0.3
3°C min–1
0.0
0 30 60 90 120 150 180 210 240

Temperature (°C)
Fig. E2.2: TPD at different heating rates.
2.2.5.3 Temperature programmed oxidation (TPO)

In temperature-programmed oxidation (TPO) the nature of solids deposited on de-
activated catalysts is analyzed, giving valuable information about the regeneration
conditions. Oxygen consumption is measured as a function of time. The method is
often used to investigate coke deposited on supported metal catalysts and zeolites
(Fig. 2.32).
In many cases, such as the one shown in Fig. 2.32 for metal (nickel and vana-
dium) containing zeolitic catalysts used in fluid catalytic cracking (discussed in de-
tail in Chapter 4), TPO profiles usually contain several peaks that reflect the form of
carbon structure on the spent catalysts. When these peaks are not well-resolved as
in Fig. 2.32, deconvolution is needed to make proper assignments.
A higher temperature peak (peak N in Fig. 2.32) is associated with more gra-
phitic- like or highly aromatic coke with high H/C ratio. Peak M is assigned to cata-
lytic coke produced by acid-catalyzed cracking, which is more reactive to oxygen
than the graphitic coke, but less reactive than the coke associated with metals
(peaks K and L).

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1500
1000
500
TCD response (a.u.)
0
530 Peak M
1000
Peak L
Peak K 439 Peak N
500 340 613
–500
0 200 400 600 800
Temperature (°C)
Fig. 2.32: TPO of coke for an equilibrated fluid catalytic cracking (FCC) catalyst after cracking of
sour heavy gas oil. [Redrawn from [14]].
2.2.6 Calorimetry
Microcalorimetry is a very useful technique – conceptually easy but difficult to imple-

ment. Typically, during the measurements adsorption isotherm is obtained simulta-
neously with calorimetric data. In a differential scanning calorimeter there are two
sample holders. Thermal behavior caused by the temperature difference between the
sample under investigation and the reference sample is recorded (Fig. 2.33).
Furnace
Reference Sample
Heat flow
Balance controller
Fig. 2.33: Sketch of a differential scanning calorimeter.
In adsorption calorimetry there is a stepwise introduction of the adsorbate at a con-

stant temperature. For each adsorption step with a slow increase of pressure the
adsorbed amount and the evolved heat must be determined. The differential heat
can then be calculated from the evolved heat in relation to the number of molecules
adsorbed in a particular step qdiff = [dQ/dn]T,A as illustrated in Fig. 2.34A, which

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demonstrates that the heat of adsorption remains approximately constant up to

nearly one-third of the monolayer, but decreasing thereafter. There is a wealth body
of experimental data for different systems (supported metals, zeolites, single crys-
tals) that confirms the decrease of the heat of adsorption with coverage. An exam-
ple is shown in Fig. 2.34B. A linear decrease in the heat of adsorption with coverage
corresponds to logarithmic (Temkin) adsorption isotherm θ = lnða0 pÞ=f
Differential heat of adsorbed CO (kJ mol–1)
60
250
55 (a) C2H2–Pd/AI2O3
50
Differential heat (kJ/mol)

45 200 C2H2–PdZn
40
35 150 C2H4–Pd/AI2O3
30
C2H4–PdZn
25
100
20
15
10 50
5
0 0
0.000 0.001 0.002 0.003 0.004 0 10 20 30 40
Adsorbed amount of CO (mmol g–1) Adsorbate amount (μmol/g)
Fig. 2.34: Differential heats of adsorption as a function of coverage for (A) CO at 40 °C on Pd/N-CNT
[15] and (B) ethylene on palladium catalysts [16]. Reproduced with permission.
2.2.7 X-ray diffraction
X-ray diffraction (XRD) is a versatile, non-destructive technique that reveals de-

tailed information about the chemical composition and crystallographic structure
of natural and manufactured materials.
Diffraction patterns are obtained from diffracted X-rays of a certain wave length
λ (for example, CuK α radiation, λ = 1.5418 Å) by rotating the ionization chamber 2θ
degrees in the scan mode within a range of 2θ values while the crystal is rotating θ
degrees. The crystal planes are then reflected. They are separated by spacing d
(Fig. 2.35A) when the Bragg law nλ = 2dsinθ is fulfilled, with reflection order n being
an integer. Diffraction patterns are compared with available databases to identify
crystalline phases present in the sample.
Because of imperfection of the crystal, noise and the interference of the back-
ground, the obtained diffractograms (Fig. 2.35B) are not perfect. Width of the peak
provides information about the crystallite size, which is inversely proportional to
the full width at half maximum (FWHM) of the diffraction peak according to a
widely used empirical Scherrer equation. Instead of the line width at half height, a
more accurate parameter is the ratio between the area of the peak and its intensity.

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Wave 8,000
front
6,000
Counts
4,000
Θ
2,000
d
0
0 2 4 6 8 10
(A) (B) 2ϴ
Fig. 2.35: XRD: (A) principle and (B) an XRD pattern for Na-MCM-41.
Commonly used catalytic supports such as silica and alumina typically have high
surface area and low crystallinity. For example, silica has broad diffraction peaks
(2θ = 20 and 25°), and also few broad diffraction peaks are obtained even for the most
crystalline aluminas. Conversely, mesoporous silicas such as MCM-41 (Fig. 2.35B)
have a high degree of organization and reflections found at small angles (below 8°).
Zeolites are crystalline materials and have very distinct diffraction patterns.
When reflections are not seen in the pattern, there could be several reasons
why. In addition to a complete absence of a certain phase, low concentrations of
the active phase could be an explanation because catalytic material should be pres-
ent in an amount larger than 1%. There could be not enough crystallinity in the ac-
tive phase, as an amorphous phase will not be distinguished from the base line.
Interference between the diffraction lines of the active phase and the support might
mask the presence of an otherwise crystalline phase. Small metal clusters (below
3 nm) cannot be detected (Fig. 2.36A), thus EXAFS is most frequently used for com-
pounds exhibiting only a short range order. Because of broadening of the peaks,
the size of metal clusters is usually overestimated from XRD analysis.
XRD can be used to study if metal sintering is happening during catalysis.
Fig. 2.36B illustrates a particular case of fatty acid hydrogenation for which there was
no sintering of palladium. It should be mentioned that not all reflections are seen in
an XRD pattern. Thus, for face-centered structures only those reflections are present,
where the values of indices (Fig. 2.36B) are unmixed (all even or all odd).
Figure 2.37 illustrates information that can be obtained from an idealized dif-
fraction pattern.
2.2.8 X-ray photoelectron spectroscopy and X-ray fluorescence
Analytical techniques, such as XPS based on the detection of ejected electrons, are
the most suitable methods for the analysis of surfaces because they probe a limited
depth of the sample (~5–10 first monolayers).

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002(C)
8000
0.8 wt%-Ir-MCM-41 (9.7 nm)

Intensity
6000 111(Pd)
200(Pd)
220(Pd)
0,98 wt%-Ir-MCM-41 (6.4 nm) Initial
4000 10(C)
004(C)
1.1 wt%-Ir-MCM-41 (propably <3 nm)
Spent
40 45 50 10 20 30 40 50 60 70
2ϴ (°) 2ϴ (°)
(A) (B)
Fig. 2.36: XRD of supported metals. (A) Ir/MCM-41 catalysts prepared by different methods. (B) Fresh
and spent (after hydrogenation of fatty acids) Pd/C catalysts. Reproduced with permission from [17].
7,000
6,000
Peak area (= integral Intensity)
→ real measure for peak intensity
5,000 → ∙ crystal structure ( contents of the unit cell
∙ phase amount ( in a phase mixture)
Intensity [counts]
4,000
Peak width
→ crystallite size, defects (strain, disorder0
3,000 ∙ full width at half maximum (FWHM),
also known as “half width”
Peak height (= maximum intensity) → peak profile dependent!
2,000
→ approximation for peak intensity ∙ integral breadth
(= Integral Intensity / maximum intensity)
1,000 → less dependent from peak profile
0
20 25 30 35 40 45 50 55 60 65 70
Peak position 2theta [°] Peak shape (peak profile)

→ d-spacing → crystallite size, defects (strain, disorder)
→ lattice parameters (metrics of the unit cell)
Fig. 2.37: Information content of an idealized diffraction pattern. Reproduced from [18]. Copyright
© 2015 Recent Research in Science and Technology.
A limit of these techniques for applications in heterogeneous catalysis is repre-

sented by the high vacuum environment required rather than real catalytic working
conditions such as atmospheric or even high-pressure environments. Nevertheless,
XPS can give valuable information regarding: catalyst composition, i.e., the elements
present; chemical nature of the elements; chemical nature of neighboring (coordinat-
ing) atoms; dispersion of active phase and support; and location of active phase in
the particle.
In XPS measurements, ionization of the inner electron shells of atoms occurs
because of exposure to monochromatic X-rays (Fig. 2.38).

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Photoelectron
Kinetic
energy
EV
ϕ
EF
Valence
band Binding
energy
Photon
Core hole
Core
levels
Fig. 2.38: Principles of XPS.
The difference between the kinetic energy of the emitted electrons and the
X-rays energy is measured, which is then related to the binding energy:
hv = EB + EKin + Ecorr (2:22)
where hv is the energy of photons, Ekin is the kinetic energy of emitted electrons, EB
is the binding energy of emitted electrons, Ecorr is the correction factor, also includ-
ing the work function ϕ.
XPS is a surface sensitive technique as only electrons close to the surface can
escape without energy loss, while those deeper in the bulk lose part of their kinetic
energy while travelling towards the surface and cannot escape.
Several peaks are expected because of the spin-orbital coupling. The binding
energy or position of a peak is specific for an element and depends on the oxidation
state (electrons are stronger bound to atoms in higher oxidation states), chemical
environment (for example, neighboring atoms, types of ligands, their number, etc.).
Position of the main peak and satellite peaks, caused by energy loss through plas-
mons, help to identify the elements, and thus XPS is often called ESCA (electron
spectroscopy of chemical analysis).
Quantitative analysis of XPS spectra takes into account the charging of the sam-
ple during measurements (and thus shift in the binding energy), which can be per-
formed by relating the peaks to a reference peak, for example, C 1s peak at
284.6 eV. In addition, when the measurements take a significant time there is a pos-
sibility of surface atoms reduction altering the ratio between the peaks correspond-
ing to different oxidation states. As an example, XPS measurements of supported Pt
catalysts that contain chlorine are presented in Fig. 2.39, demonstrating that the
ratio between Pt+2 and Pt+4 is changing during measurements.

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PtCl2 Al PtCl4
269 – 341 min (c)
75 – 245 min (b)
30 – 75 min (a)
68 69 70 71 72 73 74 75 76 77 78 79 80
Binding energy (eV)
Fig. 2.39: Pt 4f photoelectron spectra of 5 wt% Pt/silica fibers catalyst during prolonged X-ray
bombardment.
As already apparent from Fig. 2.39, deconvolution of XPS spectra with the con-
tribution of several oxidation states can be challenging.
XPS data could be also used for determination of the metal particles size esti-
mations based on the dispersed phase/support phase XPS intensity ratio, as elabo-
rated by Davis [19].
X-ray fluorescence (XRF), widely used for elemental analysis, is the emission of
characteristic “secondary” (or fluorescent) X-rays from a material that has been ex-
cited by bombarding with high-energy X-rays or gamma rays (Fig. 2.40). The term
“fluorescence” is applied to phenomena in which the absorption of higher-energy
radiation results in the re-emission of lower-energy radiation.
2.2.9 Infrared and Raman spectroscopies
Vibrational spectroscopies are applied in order to study chemical bonds in chemi-

sorbed species as well as the solid substances. In the IR domain (200–4,000 cm−1)
the absorption of energy excites bonds to a higher vibrational state with only excita-
tions modifying the dipolar moment taking place. Different chemical bonds absorb
IR-light at certain wave lengths and the absorbed intensity can be analyzed, allowing

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hν
hν
Fig. 2.40: Principles of X-ray fluorescence.
characterization of the bonds. Typically emissions of a fast pulse of light are analyzed
by Fourier transform (FTIR). Transmission mode is applied for transparent samples
(Fig. 2.41), which are either self-supported or KBr diluted wafers prepared under me-
chanical pressure.
IR
IR
Transmission Diffuse reflectance
Fig. 2.41: IR spectroscopy arrangements.
Transmission is widely applied for solids and the spectrum is a result of the trans-
mission of catalyst vs transmission of a reference. In diffuse reflectance mode
(DRIFTS) catalyst grains are dispersed in a diffusing matrix, whose spectrum should
be subtracted.
Infrared spectroscopy can be used for catalyst characterization by, for exam-
ple, direct measurement of catalyst IR spectrum and analyzing positions of OH
groups, as these positions and shapes provide information about the coordination
(Fig. 2.42).
Measurements of interactions with probe molecules, such as ammonia, acetoni-
trile, tert-butylnitrile or pyridine, allow the determination of catalysts acidity, while
basic sites could be probed with, for example, CO2. There is a long tradition dating
back to the 1950s and 1960s of using IR studies of adsorbed ammonia and pyridine
molecules for the characterization of solids. The advantages of ammonia as a probe
molecule for acidity are related to the molecule size, which is able to penetrate even
very narrow pores and small cages of zeolites. Moreover, ammonia does not con-
taminate vacuum installation. However, ammonia forms dimers and the spectra are
not as well-resolved as for pyridine adsorption. Fig. 2.43 illustrates adsorption of
ammonia and pyridine on proton (Brønsted, H+) and Lewis (L) sites. The band

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Vicinal Isolated Geminal

H
H H
H
O O O
O O
Si Si Si Si
O
3,720, 3,520–3,720 cm–1 3,750 cm–1 3,742 cm–1
Fig. 2.42: Silanol groups on amorphous silica.
NH4+
1,450
N
PyL
1,450 Lewis acid
NH3L
1,620
PyH+
1,545
1,700 1,600 1,500 1,400 cm–1
Fig. 2.43: IR spectra of ammonia and pyridine adsorption on Brønsted and Lewis acid sites.
intensity should be related to the concentration of acid sites by applying extinction

coefficients.
Although pyridine is most frequently used for qualitative and quantitative acid-
ity studies its disadvantage is related to the size, disallowing entrance to pores
smaller than 0.5 nm. Acetonitrile, another often-used probe molecule, is not basic
enough although it is small.
IR can be also used to elucidate metal dispersion. Fig. 2.44 shows adsorption of
Pt/Si-SBA–15 catalyst, the data were obtained at University of Pierre and Marie Curie.
A band at 2,079 cm−1 is characteristic for CO linearly adsorbed on Pt nanoparticles,
while bridging CO bands adsorbed on two Pt atoms (1,860 cm−1) are favored on larger
faceted Pt particles. Thus, judging by low intensity of the latter signal, it can be stated
that large particles of Pt are absent and the catalyst is highly dispersed.
Note that the investigation of catalysts with high metal loadings is problematic
because of low transmission.
FTIR is widely applied in mechanistic studies, allowing the analysis of ad-
sorbed substrates, reaction intermediates and deactivation, as well as in situ reac-
tion monitoring. Fig. 2.45 illustrates FTIR spectra obtained by flowing a mixture of

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0.08
0.07 Pt-CO
2,079
0.06
Si-OH-CO
0.05 2,157
Absorbance
0.04
0.03
0.02
Pt2-CO
0.01
1,860
0.00
2,300 2,200 2,100 2,000 1,900 1,800 cm–1
Fig. 2.44: Adsorption of CO on Pt/Si-SBA–15.
1.4
1,605
1,250
1,295
1,550
1.2
1.0
Absorbance
0.8
NO + O2 (80 min)
0.6 NO + O2 (60 min)
NO + O2 (40 min)
0.4
NO + O2 (15 min)
0.2
NO + O2 (6 min)
0.0 NO + O2 (1 min)
2,500 2,000 1,500 1,000 cm–1
Fig. 2.45: Time-on-stream in situ FTIR on Ag/alumina at 250 °C in a flow of 1,000 ppm NO and
6 vol% O2 in He. (Reproduced with permission from [20]).
NO and oxygen through a silver on alumina catalyst. Slow formation of the peaks at
1,250, 1,295 and 1,550 cm–1 and a shoulder at 1,605 cm−1 is attributed to generation
of monodentate nitrate (1,250 and 1,550 cm−1) and bidentate nitrate (1,295 and
1,605 cm−1).

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As a general comment on in situ and operando spectroscopies, not all observed

species participate in the reaction, and some spectator species could be registered
just because they do not react.
In addition to IR, ultraviolet-visible spectroscopy in the ultraviolet-visible spectral
region (50,000–2,500 cm−1) is also frequently applied for the analysis of solid catalysts
and adsorbed species. It uses light in the visible and adjacent ranges (near-infrared,
12,500–3,300 cm−1). UV-vis spectra obtained in situ at the Fritz Haber Institute during
isomerization of n-butane on mordenite zeolite [12] show bands at 250–370 nm
(Fig. 2.46) that are ascribed to neutral conjugated double-bond oligomers, while bands
at 370–500 nm correspond to carbocationic oligomers.
1.0
293
~4 h
0.8
Kubelka Munk function
2h
0.6
1h
0.4
330
0.2 395 450

Activated
0.0
250 300 350 400 450 500 550 600
Wavelength (nm)
Fig. 2.46: UV-vis spectra in butane oligomerization over H-mordenite at 534 K with n-butane/
nitrogen ratio 5:95. Reproduced from [21].
While reflectance or transmission is transformed into adsorbance in FTIR (Fig. 2.45),

in UV-vis the Kubelka Munk transform is applied in diffuse reflectance (Fig. 2.46),
relating the ratio between the absorption coefficient and the scatter coefficient of
the sample at a given wavelength to reflectance.
A variation of IR is attenuated total reflectance (ATR) that enables samples to be
examined directly in the solid or liquid state without further preparation (Fig. 2.47).
Contrary to IR, Raman spectroscopy relies on different wavelengths of the scat-
tered light, which is a feature only of a small fraction (10−6) of emitted light. The
selection rules are also different in Raman and IR spectroscopies, and some types of
molecular motions appear in Raman and IR, and some only in Raman or IR. Namely,
a criterion for Raman scattering is polarizability, while for IR it is a transition in the

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Sample in contact
with evanescent wave
To detector
Infrared
beam ATR crystal
Fig. 2.47: Schematic of ATR-IR. (Reproduced from [21].)
vibrational states that induce a change in the dipole moment. A particular vibration
mode in Raman is silent if polarizability is not changed by vibration.
Raman spectroscopy is more useful for studying the catalyst itself and since
water does not interfere with Raman spectroscopy it could be used in aqueous sys-
tems, where IR is difficult. Conventional Raman signals have lower sensitivity that
requires an enhancement, which is achieved by applying lasers. Raman spectros-
copy can be combined with “operando studies”, where the spectra of the catalyst
are measured during a catalytic reaction (Fig. 2.48).
Operando reactor
Catalyst Thermocouple well
Inert packing
Online gas Raman system NH3

chromatograph Renishaw system 1000 Vent
Gas feed
system O2
Heat C3H8
screen
He
Heating element Temperature

controller
Operando system
Fig. 2.48: Operando system. (Reproduced with permission from [22].)

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IR-visible SFG spectroscopy has recently started to be applied for catalytic materi-
als. It uses two input laser beams overlapping at the surface of a material, generating
an output beam with a frequency that is the sum of the two input beams. One of the
two input beams is a visible wavelength laser at a constant frequency, while the
other is from infrared laser that is tuned to scan the system and obtain the vibrational
spectrum (Fig. 2.49). SFG has the disadvantage of a relatively small frequency range
(1,600–4,000 cm−1) and lower resolution and sensitivity, compared with IR.
Vi
sib
Tun
le
ab
le I
la
R la
se
ser
rω
ω ω sum
Vi
IR
s
Sample surface
Fig. 2.49: Principle of IR-visible sum frequency generation spectroscopy.
Conversely, this method affords the possibility of obtaining vibrational spectra

in situ at both buried and exposed interfaces, as well as under equilibrium and reac-
tion conditions. This is in contrast to traditional vibrational spectroscopies when
signals are generated from the surface.
2.2.10 Catalyst particle size measurements
The mean particle size of a catalyst can be determined by a light scattering tech-
nique using a laser diffraction and commercially available particle size analyzers.
The determination is based on He-Ne laser light scattering as light is passed
through the particle suspension. The scattering profile is collected by a Fourier
Transforming lens and the various outputs are handled and converted to particle
size distributions by an integral computer.
The particles size of powdered catalysts can be measured using a counter type
apparatus that has one or more microchannels that the separate two chambers
containing the electrolyte solutions. When a particle flows through one of the mi-
crochannels, it results in the electrical resistance change of the liquid-filled micro-
channel. This resistance change can be recorded as electric current or voltage
pulses, which can be correlated to size, mobility, surface charge and concentra-
tion of the particles.

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2.2.11 Electron paramagnetic/spin resonance
The technique relies on resonant absorption of microwave radiation by paramag-

netic ions or molecules with at least one unpaired spin in the presence of a static
external magnetic field. From an experimental perspective, the measurements are
organized by keeping the wavelength constant and recoding variations in the mag-
netic field. As a result, complex spectra in a narrow range of energy are obtained
with the superposition of different paramagnetic species and several spectra com-
ponents caused by anisotropy of the environment.
EPR is applied for structural characterization of solid and liquid systems and
only radicals (species with unpaired electrons) can be detected. Transition metal
cations in specific oxidation states (for example, Cr3+ d3, F3+ d5 high spin), O– and
O2 are most relevant to catalysis.
Signal positions depend on the electron configuration of the molecule or cat-
ion and on the energy difference between the d orbitals for paramagnetic transition
metal cations. Delocalization of electrons on metal ions and ligands is reflected
from the number of lines and their intensities, while coupling constants provide
information on the bonding between the cation and the ligands. In addition, probe
molecules can be used to study the species present in the catalyst. For example,
Fig. 2.50 shows the ESR spectra recorded at 77 K for the fresh iron-modified beta
3,000
ESR spectra 4.Fe-Beta-25 IE
recorded at 77 K
2,000 g = 4.25
1,000
g = 1.99 Fresh sample
–1,000 g = 4.25
Intensity (a.u.)
After evac at 673 K 4 h
–2,000 g = 2.0023
g = 4.26
–3,000
g = 3.93
–4,000 After 1 doz of NO
and evac at RT 5 min
–5,000
–6,000
0 100 200 300 400 500
Field (mT)
Fig. 2.50: ESR spectra of fresh, evacuated and NO adsorbed Fe-H-Beta-25 (Reproduced with
permission from [23]).

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zeolite, for the same material after evacuation at 300 °C for 4 h and after adsorp-
tion of NO.
The ESR spectrum for the fresh sample displays signals in two different re-
gions of the magnetic field, a broad line that can be assigned to randomly oriented
Fe3+ ions in oxides and/or hydroxides species. The signal at g = 4.25 in a low field
region originates from Fe3+ ions in tetrahedral coordination. After evacuation at
673 K for 4 h a signal at g = 4.25 is more visible and a signal from iron oxide and
hydroxide species is less intensive. The new narrow ESR signal (g = 2.0023) can
originate from coke formed from residual template, but it also can be caused by
Fe3+ in octahedral coordination, as isolated ions in cationic position attributed a
sharp line at g = 2 to superoxide ions (O2 − ) that are associated with iron ions.
Adsorption of NO results in ESR signals in the magnetic field range 300–350 mT
and in another one in the low field (g = 3.9). After short evacuation a rhombic sig-
nal appears, with three distinct values of the diagonal terms (g = 2.09, g = 2.06,
g = 2.02). The low field value (g = 3.93) originates from (NO)2 biradicals. Based on
this, it can be assumed that most of the iron is tetrahedral Fe3+ but that some Fe2+
is also present.
In addition to the identification of paramagnetic species on the surface or
within cavities of zeolites/mesoporous materials, EPR can be used for identification
of radicals, which could escape into the gas-phase. Such events could occur, for ex-
ample, in partial oxidation of hydrocarbons or in hydrocarbon-assisted SCR of NOx
in which the generation of radicals was detected by matrix isolation EPR [24].
Propagation of the surface reactions into the gas-phase is beneficial for the overall
NOx conversion and could be used in engineering of catalytic converters. For exam-
ple, a catalytic unit for reduction of NOx can contain several catalytic beds
(Fig. 2.51; 3a–3e), that are arranged separately from each other in a longitudinal di-
rection in the catalyst unit, and a number of second reaction zones (Fig. 2.51;
4a–4e) downstream of each respective catalytic bed.
2 5 4a 4b 4c 4d 4e 7 6
L1
L2
1 3a 3b 3c 3d 3e
Fig. 2.51: Catalytic converter. 1, catalytic unit; 2, exhaust pipe; 3, catalytic zones; 4, gas-phase
reaction zones; 5, inlet; 6, outlet; 7, oxidation catalyst. (Reproduced from [25]).

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2.2.12 Mössbauer spectroscopy
Mössbauer spectroscopy provides information about the oxidation state, coordina-

tion number, ligand type, electron distribution, the strength of binding to the sur-
rounding of the resonant atom and the electric charges of the neighbors. The
technique is based on absorption by a nucleus of the resonant atom of photons
emitted by a radioactive source (for iron this is 57Co). The wavelength emitted has a
constant value, which is slightly varied by the Doppler effect, i.e., by moving the
gamma-ray source towards and away from the sample at varying speeds, typically a
few mm s−1 (Fig. 2.52). For convenience, Mössbauer spectra allowing observations
of the hyperfine interactions correspond to the intensity of the transmitted X-rays
as a function of the Doppler velocity.
Radioactive Sample Detector

source
Fig. 2.52: Mössbauer apparatus.
During emission or absorption of photon a free nucleus recoils because of the con-
servation of momentum with a certain recoil energy. Resonance is achieved when
the loss of the recoil energy is overcome by having the emitting and absorbing nu-
clei in a solid matrix. Identical environments of emitting and absorbing nuclei pro-
duce a single absorption line spectrum, as shown in Fig. 2.53. As the resonance
occurs only in the case of exact matching the transition energies of the emitting
and absorbing nucleus the effect is isotope specific.
Emitter nucleus Absorber nucleus
g g
Detector
Fig. 2.53: Simple Mössbauer spectrum from identical source and absorber.

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The strength of the signal reflects the relative number of recoil-free events and is
dependent upon the γ-ray energy, thus the Mössbauer effect is only detected in iso-
topes with very low-lying excited states. The resolution is dependent on the lifetime of
the excited state. Because of these constraints the technique is limited to a few iso-
topes, including (relevant for catalysis) 57Fe, 119Sn. For isotopes such as 193Ir or 197Au, a
very short lifetime of a radioactive source prevents their characterization by Mössbauer
spectroscopy.
When the source and absorber are identical the absorption peak is seen at zero
velocity (0 mm s−1), while various types of changes in the environment of the reso-
nant atoms lead to changes in the spectra. The isomer shift, which is useful for de-
termining valence states, ligand bonding states and electron shielding, is caused by
changes in the s-electron environment, allowing differentiation between Fe+2 and
Fe+3 for example.
The nuclear energy levels are split (quadruple splitting) in the presence of an
asymmetrical electric field caused by asymmetric electronic charge distribution or
ligand arrangement. Magnetic splitting of nuclear levels with a spin of I in the pres-
ence of a magnetic field into (2I + 1) substrates is caused by dipolar interactions of
the nuclear spin moment with the magnetic field.
Thus 57Fe Mössbauer spectroscopy is the method for the study of valency, coordi-
nation and magnetic properties of the iron species in for example iron-modified zeo-
lites, contrary to the limited abilities of ESR or IR. In these materials, in addition to
extra-framework iron species (for example, not isomorphously substituted), isolated
Fe ions with a different oxidation state that are chemically anchored to the frame-
work via –O–Fe bridges, are present in addition to dinuclear Fe-O-Fe species con-
fined in the channels, oligomeric Fe oxi species in the large cavities and oxide-like
clusters. Typically, 57Fe Mössbauer spectra (see Fig. 2.54) are fitted to get the best cor-
respondence with the data by using the line width peak intensity, isomer shifts and
100
100
98
Transmission (%)
Transmission (%)
99.8 96
94
99.6
92
90
–2 –1 0 1 2 –10 –8 –6 –4 –2 0 2 4 6 8 10
(A) Velocity (mm s–1) (B) Velocity (mm s–1)
Fig. 2.54: Room temperature 57Fe Mössbauer spectra of (A) Fe-ZSM-5 prepared by ion exchange and
(B) spectrum with sextet: α-Fe2O3. (Reproduced with permission from [26]).

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the quadruple coupling constant as fit parameters. The quadruple coupling constant
measures the splitting in mm s−1 between the two lines in the doublet.
Fig. 2.54(A) displays 57Fe Mössbauer spectra consisting of a single paramagnetic
doublet for Fe-ZSM-5 zeolite, prepared by ion exchange. In fact, the shape of spectra
depends very much on the preparation methods. In the case of ion exchange prepara-
tion methods the presence of Fe3+ ions in octahedral coordination gives intense central
doublets (0.3 < isomeric shift < 0.4 mm s−1 and 0.5 < quadruple splitting < 1.1 mm s−1),
while the appearance of additional doublets with the isomeric shift ~1.2 mm s−1 and
1.5 < quadruple splitting < 2.8 mm s−1 (absent in Fig. 2.54A) is associated with Fe2+ ions
in an octahedral coordination. Agglomerated iron oxide species could result in a sextet
(absent in Fig. 2.54A, but present in Fig. 2.52B).
If Fe-ZSM-5 is prepared by isomorphous substitution a broad singlet with an
isomer shift of 0.52 mm s−1 will be observed in the spectra, corresponding to tetra-
hedrally coordinated high spin Fe3+ ions and reflecting the incorporation of iron
into the framework. If the same catalyst is calcined, migration of iron to an extra-
framework position and increased interactions between extra-framework Fe3+ and
the zeolite lattice will lead to an unresolved doublet in the Mössbauer spectrum.
Alternative methods of Fe-ZSM-5 catalyst preparation (impregnation, reductive
solid state ion exchange and chemical vapor deposition) result in spectra, which
could be deconvoluted into a hyperfine magnetic sextet and two quadruple doublet
lines, confirming the presence of large α-Fe2O3 particles and either small α-Fe2O3
particles or Fe3+ in a strong distorted environment.
2.2.13 X-ray absorption spectroscopy
This is an element-specific type of spectroscopy that requires synchrotron produced X-

rays with energy close to the absorption edge of the element core shells. Information
about the oxidation state of the element is retrieved from the edge (Fig. 2.55) as the
edge shifts to higher energy with an increase of oxidation state.
X-ray absorption near-edge spectroscopy (XANES, Fig. 2.55), in addition to al-
lowing elucidation of the oxidation state, also provides information on the electro-
negativity of the neighboring atoms and symmetry of the atomic environment.
Electrons from the K edge correspond to s-orbitals, while the L edge corresponds to
p-orbitals. EXAFS is used to acquire information on the coordination shells around
the atom, number of surrounding atoms, bond lengths, dynamic and static disorder
in the inter-nuclear distances. It is especially useful for materials without long-
range organization when XRD cannot be applied. The waves of atoms interfere with
the wave of the emitted after-ionization electrons, resulting in absorption oscilla-
tions seen in EXAFS spectra. Fourier transform is applied to decompose the EXAFS
signal. Each peak in Fig. 2.56, presented here for illustration, corresponds to a shell
of scattering atoms at a certain distance. A number of parameters is needed for the

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2.0
Normalized absorption
EXAFS 1.6
Absorption (a.u.)
4
3
1.2
2
1
XANES 0.8 1 PdO
2 2% Pd/HBETA-300, 120°C, He
3 3.9% Pd/HBETA-150, 120°C, He
0.4
4 4.7% Pd/HBETA-25, 120°C, He
5 4.1% Pd/HBETA-22, 120°C, He
0.0
Energy (eV) 24,300 24,400 24,500 24,600
(A) (B) Photon energy (eV)
Fig. 2.55: X-Ray absorption spectroscopy. (A) XANES and EXAFS regions. (B) Pd K-XANES spectra of
calcined Pd/H-beta catalysts and PdO.
1
FT (Xk2)
–1
–2
–3
0 1 2 3 4
Uncorrected distance (Å)
Fig. 2.56: Model fits of Pd K EXAFS spectra taken from a calcined 2% Pd/H-beta-300 catalyst.
data fitting thus precise simulation is challenging especially when too many differ-
ent atoms and/or distances coexist. Blurring of a signal is possible when there is
too large a discrepancy in the atom environment, as the EXAFS signal is an aver-
aged linear combination of all sites of a particular element.
2.2.14 Nuclear magnetic resonance
Nuclear magnetic resonance (NMR), being isotope specific, concerns isotopes with
a nuclear spin different from zero. It is based on splitting of the nuclear spin ground
level by an external magnetic field of constant value and the subsequent absorption

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of energy from electromagnetic radiation of varying wavelengths. Absorption signal

positions (chemical shift) depend on the nuclei electron environment shielding nu-
cleus spin from the external magnetic field. For a nuclear spin I the number of lines
is 2nI + 1, which are separated by a coupling constant, the latter linked to the dis-
tance between the nuclei. The inherent sensitivity of NMR is low, although it is pos-
sible to get larger signals by using highly dispersed or porous materials. For the
solid materials, broadening of the signals is overcome by rotating the sample 54.74°
with respect to the magnetic fields (magic angle spinning, MAS).
1
H NMR is applied for the characterization of OH groups, while 13C NMR can
be used for studying adsorption of isotopically marked organic compounds. The
chemical shifts in 29Si MAS NMR are linked to the number of silicon atoms pres-
ent as second neighbors. An example of the 29Si MAS NMR spectra for a mesopo-
rous material H-MCM-41 is given in Fig. 2.57, showing several broad overlapping
lines. A computer fit to the spectrum gives the lines at −108.5 ppm (65% of the
total intensity), −100.6 ppm (13%), −94.8 ppm (19%) and −80 ppm (3%). The
strongest peak at −108.5 ppm can be attributed to Si(OSi)4 sites, while the com-
ponents at −100.6, and −94.8 ppm are caused by the sites with silanol groups Si
(OSi)3OH and Si(OSi)2(OH)2, respectively. As the material has a considerable
amount of Al in the framework, the contribution to the signal is expected from
the sites Si(OSi)3(OAl), Si(OSi)2(OAl)2, Si(OSi)(OAl)3, and Si(OAl)4 in the region
of −80 ppm to −100 ppm.
Intensity
Intensity
0 –40 –80 –120 –160 –200 200 150 100 50 0 –50 –100
ppm ppm
Fig. 2.57: 29Si (left) and 27Al (right) MAS NMR spectra of H-MCM-41 including the computer fits.
(Reproduced from [27] with permission from the PCCP Owner Societies).
The 27Al MAS spectrum of H-MCM-41 (Fig. 2.57) shows a signal with a maximum at
54 ppm caused by tetrahedrally coordinated framework aluminum and a broad
asymmetric line around 0 ppm caused by octahedrally coordinated aluminum sites.

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A small component arising from the computer fit was attributed tentatively to the
distorted tetrahedral or five-coordinated Al sites. The quantitative analysis of the
spectrum yields the overall absolute number of Al sites, as well as the respective
values for framework tetrahedral, non-framework tetrahedral or five-coordinated
and octahedral aluminum. The Si/Al ratio can be estimated from the 27Al line
intensity.
NMR can also be used to characterize microporosity of zeolites applying 129Xe,
whose chemical shifts depend on the inner void structure of the solid and charge
gradients.
2.2.15 Imaging of catalysts
Several techniques are applied for the imaging of catalysts.
2.2.15.1 Electron microscopy [28, 29]

Electron microscopy uses a particle beam of electrons to illuminate a specimen and
create a highly-magnified image (Fig. 2.58). Electron microscopes have a much
greater resolving power and can obtain much higher magnifications than light mi-
croscopes that use electromagnetic radiation. Electron microscopy is usually com-
bined with elemental (EDX) or structural analysis (XRD). In EDX X-rays are emitted
by the atoms for which inner shell energy levels are ionized by electron excitation
and then collected.
Primary electron beam Cathode

Anode
EDX, WDX Lens
X-rays Backscattered electrons

Sample
Secondary lens
electrons SEM
Photons Auger electrons
Image
TEM, lens
dark field Diffracted Loss
electrons electrons
Transmitted TEM,
electrons bright field Final image
Fig. 2.58: Different electron microscopes. (Reproduced with permission from [29]).

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The TEM uses a high voltage electron beam (100–300 keV) to create an image.
The electrons are emitted by an electron gun and the electron beam is accelerated by
an anode focused by electrostatic and electromagnetic lenses, and transmitted
through the specimen that is in part transparent to electrons and in part scatters
them out of the beam. The magnification range in TEM is 102–107. The sample is put
on a grid and is placed in a vacuum chamber. Images are formed because of different
lateral absorptions of the beam, with heavy atoms being darker. A 10–7 Torr is usually
used for high-resolution electron microscopy to avoid noise caused by gas molecules.
The practical limit of detection is ~1 nm, although several times lower resolution is
possible. Support and the supported phase are distinguished where there is good
contrast between them (Fig. 2.59). Discrimination of the two phases is easier when
their d-spacing and shape are different. Oxide supports are more difficult to distin-
guish than the metallic phase. The same difficulty applies to metals of the first transi-
tion row compared to heavier metals from the third row. Challenges in images are
also present in the case of poorly organized supports, such as γ-alumina, which ex-
hibits agglomeration of small crystallites, and on well-crystallized supports with
many d spacings in images.
3 nm
Fig. 2.59: A metal cluster on a support: TEM image.
For small particles with poor contrast with the support, good images are obtained
when electrons are scattered at high angles, which is far from the position of the
objective aperture in classical TEM. In the case of high-angle annular dark field
(HAADF) metal particles are visible as bright sports over a dark background.
For calculation of cluster size distribution (Fig. 2.60) and the average size of
particles, several hundreds of clusters are counted that counterbalance premature
conclusions based on eye-catching zones (unexpectedly large particles or unusual
particle shape).

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40
30
Frequency (%)
20
10
0
0 1 2 3 4 5 6 7 8 9 10 11 50 nm
(A) Particle size (nm) (B)
Fig. 2.60: HRTEM of Au/Al2O3 catalyst. (A) Image. (B) Cluster size distribution.
Another recent development in HRTEM is associated with 3D imaging, when

the sample is tilted with a small (1°) increment and the images are taken after each
change.
Although HRTEM analysis became very popular and is widely applied, it is im-
portant to remember the challenges and shortcomings associated with the method,
such as the inability of imaging of clusters well below 1 nm, representativity of the
specimen area, potential damage during preparation as well as electron beam dam-
age. High energy of the incident electron beam may cause changes in the micro-
structure of crystallites or the reduction of surface ions. Applicability of TEM for
in situ studies is limited by losing resolution at above ~5 mbar. In fact, all electron
microscopy techniques rely on high vacuum because of the large attenuation of the
electron beam in any atmosphere.
In general as technically relevant catalysts should be studied under certain gas
atmospheres it is difficult to extend vacuum-based techniques, including TEM, to
in situ experiments.
SEM has a magnification range 10–105. SEM produces images by probing the
specimen with a focused electron beam (accelerating voltage 4–30 keV) that is
scanned across a rectangular area of the specimen. Electrons emitted or scattered
by the sample are then detected. Generally, the image resolution of SEM is about
one order of magnitude poorer than that of a TEM. Fig. 2.61 shows SEM images for
ZSM-5 zeolite.
Scanning transmission electron microscopy (STEM) is a merger of TEM and
SEM, allowing the same resolution as TEM and the ability to perform microanalysis
at a high resolution similar to SEM.

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5 µm
Fig. 2.61: SEM image of zeolite ZSM-5.
2.2.15.2 Scanning probe microscopy

In scanning probe microscopy the very sharp probe is brought in contact with a sam-
ple. In scanning tunneling microscopy (STM) the probe does not touch the surface
(Fig. 2.62A). A constant tunneling electric current is maintained, and the method is
thus limited to conducting materials. Very high resolutions (height 0.01 nm, length
0.1 nm) can be achieved.
Laser
– Battery +
Current Laser
detector
Mirror
Tunneling current
Computer
Microscope tip
Sample
Sample surface scanned
(A) (B) back and forth Display
Fig. 2.62: Principles of (A) STM and (B) atomic force microscopy (AFM). (Modified from [29]).
STM studies of catalytic systems under realistic conditions (high pressure and high
temperature) are possible and have been recently achieved.
In AFM the probe can touch the surface (Fig. 2.62B). As a constant small force is
maintained the method is not limited to conducting materials and is suitable for all

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surfaces. The method allows a high resolution (length 2–10 nm, height 0.1 nm).
Desulfurization reactions in oil refining are an example of applying STM to cataly-
sis. Triangular MoS2 nanoparticles have sulfur atoms located in the edges, which
react with hydrogen, forming hydrogen sulfide. The resulting vacancy is replaced
by sulfur from the sulfur-containing oil molecules. STM studies by F. Besenbacher
and co-workers [30] (Fig. 2.63) demonstrated that the morphology of MoS2 nanopar-
ticles strongly depends on their size. When the particles contain less than 100
atoms, the relative sulfur content increases above the stoichiometric value for the
bulk MoS2. Subsequent changes occur in the edge structure to counterbalance this
increase and to lower sulfur to a molybdenum ratio and improve stability of the
nanoparticles that is deteriorating with sulfur increase. Refer to a review article [31]
for a discussion of the progress in the application of scanning probe microscopy in
catalysis.
Fig. 2.63: STM of MoS2. (Modified from [30]).
2.2.15.3 Electron microprobing

Determination of an active phase profile in catalysts grains can be performed using an
electron probe microanalyzer, which is an analytical tool used to non-destructively
determine the chemical composition of small volumes of solid materials. It works in a
similar way to SEM by bombarding the sample with an electron beam and collecting
the signals coming from the sample.
Another non-destructive method is based on applying XPS with a variation of
the emission angle.
Destructive methods involve mechanical and chemical erosion by, for example,
progressively removing surface atoms caused by ion bombardment. Another tech-
nique is laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS),
which combines the micrometer-scale resolution of a laser probe with the speed,
sensitivity and multi-element capability of ICP-MS, and rivals other microbeam

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techniques such as the proton microprobe and secondary ion mass spectrometry. A
pulsed laser beam is used to ablate a small quantity of sample material, which is
transported into the Ar plasma of the ICP-MS instrument by a stream of Ar carrier
gas. Fig. 2.64 gives an example of LA-ICP, showing an LA-ICP-MS spectrum for
Cu-H-MCM-41. The intensity of copper is following the Al-content, suggesting that
copper species are balancing the framework charge, and thus were ion-exchanged
into H-MCM-41. Some minor heterogeneity of the aluminum distribution in the sam-
ples is visible. Intensity fluctuations are also observed in the copper contents and
few intensive peaks in the sodium intensity are observed, indicating that traces of
sodium are still present in the samples that were synthesized first as Na-MCM-41
and then exchanged with protons.
Intensity (counts s–1)
Al
Cu
Na
0 20 40 60 80 100 120 140 160 180

Time (s)
Fig. 2.64: LA-ICP of Cu-H-MCM-41. (Reproduced from [27] with permission from the PCCP Owner
Societies).
2.2.15.4 Magnetic resonance imaging

In spatially unresolved conventional NMR a nucleus of non-zero nuclear spin
quantum number is placed in an external magnetic field. By exposing the system
to an electromagnetic energy of appropriate radio frequency a resonant absorp-
tion occurs between non-degenerate nuclear spin energy levels at a frequency
proportional to the strength of the external magnetic field. The precise energy-
level splitting, specific to a given isotope, is slightly modified by the electronic
environment of the nuclei, making it possible to identify the presence of particu-
lar molecular species.
In order to obtain spatial resolution a spatially varying magnetic field is applied
in addition to the large static field, with the resonance frequency of species within
a sample becoming a function of position and strength of the applied gradient.

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In pulse encoding methods, an initial and a subsequent pulsed field gradient

are applied after a certain observation time, allowing the monitoring of the distance
travelled during a known time and thus the measuring of diffusion, dispersion and
flow processes.
Magnetic resonance imaging can be used for micro-imaging of a single catalyst
pellet with a spatial resolution of ~30–50 μm, making it possible to reveal the effect
of the catalytic manufacturing process on the catalytic pellet micro- and meso-scale
structure, for example, tortuosity. At the same time, this spatial resolution does not
make it possible to resolve individual pores in a pellet. MRI can be applied to char-
acterizing metal ion distribution in the pellet during the catalyst preparation and in
the final material, as well as to spatial distribution of coke in a spent catalyst pellet.
It is possible to investigate internal phase distribution and liquid flow fields in-
side fixed-bed reactors and monoliths reactors at spatial resolution of 100–500 µm,
although measurement constrains do not allow for the study of large-scale indus-
trial size reactors.
In the case of trickle bed reactors, two-phase flow investigations make it possi-
ble to measure the values of hold-up and wetting of the catalytic materials, consis-
tent with gravimetric data and model predictions.
Fig. 2.65 shows that full pre-wetting of the bed was followed by immediate es-
tablishment of the trickle flow, yielding significantly larger catalyst wetting and
hold-up compared to other methods of wetting.
Fig. 2.65: MR images of gas and liquid distribution within a

fixed-bed reactor operating at air and water velocities of 66 and
4.6 mm s–1, respectively. The bed was fully pre-wetted. Red,
gray, and black pixels identify water, air, and packing
elements, respectively. (Reproduced with permission from [32]).
In addition to MRI related to catalytic engineering, recently there has been an inter-
est in the imaging of reactions in situ.
2.2.15.5 Positron emission tomography imaging

Positron emission tomography (PET) is now a well established diagnostic technique
in nuclear medicine, generating 3D images of radiolabeled molecules distributed
within living human organs.

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Positron-emitting short-lived radioisotopes such as 11C (half-life 20.4 min) must

be produced on-site, which is done by the irradiation of an appropriate target mate-
rial with energetic beams of protons or deuterons generated by a cyclotron.
Encounters between positrons and electrons lead to their mutual annihilation and
resulting electromagnetic radiation. Rotating a tomograph during a scan (~10–15)
allows for recoding photons emitted over 360° in the plane, making it possible to
have a 3D reconstruction of the imaged object.
Data for 11C methanol transformations in a catalytic bed of a zeolite are presented
in Fig. 2.66. The image was acquired with a small PET scanner, developed by
E. Sarkadi-Priboczki and co-workers from the Institute of Nuclear Research in
Debrezen. Red and yellow colors correspond to higher radioactivity, while green and
blue are related to lower radioactivity concentrations. The 3D image exhibits an inho-
mogeneous distribution of compounds on the catalyst, reflecting non-uniformity of
the catalyst bed in terms of activity.
11C-methanol
3D image
Fig. 2.66: 3D image of methanol conversion on a zeolitic material at 620 K. Courtesy of Dr. E. Sarkadi-
Priboczki.
2.2.15.6 Integrated laser and electron microscopy

In fluorescence microscopy (FM) a focused laser light scans a catalyst, detecting
fluorescence emission from the focal points. The technique (contrary to electron
microscopy) has limited spatial resolution and only reveals fluorescent structures.
The integrated laser and electron microscope (iLEMI developed by B. Weckhuysen
and co-workers [33]) is an imaging tool, combining the strengths of both methods.
In order to generate a fluorescence signal, fluorogenic thiophene oligomerization
is used, catalyzed by the acidic sites of the zeolites. The product, oligomerized
thiophene, emits green fluorescence with the intensity of the fluorescence relating

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to acidity. In this way a spatial resolution of ~20 nm can be achieved. The iLEM
set-up shown in Fig. 2.67A consists of a custom-designed laser scanning FM
mounted on a side port of a TEM with the laser beam perpendicular to the path of
the electron beam. For FM imaging the grid with the catalyst sample is rotated to
face the laser beam, while FM is partially retracted and the grid is tilted to enable
TEM imaging.
The technique was applied to study a fluid catalytic cracking catalyst, which
will be discussed in detail in Chapter 4. The active phase, zeolite Y, is embedded in
a matrix consisting of clay, silica, and alumina. Using iLEM, the catalyst acidity,
which is related to fluorescence intensity, could be correlated to the catalyst parti-
cle structure. Two different areas were found in the catalyst, one associated with
the zeolite component giving the fluorescent products, while the other areas are
mainly composed of the matrix material (Fig. 2.67B,C).
TEM TEM
FM FM
(A)
(B) (C)
Fig. 2.67: (A) The iLEM set-up, and iLEM analysis of a sectioned FCC catalyst particle. (B) FM image.
(C) TEM image, taken from the same region. (Reproduced with permission from [33]).
When the zeolitic structure is exposed to steam, Al atoms from the framework can
be extracted, creating extra-framework Al species. This results in lower amounts of
Brønsted acid sites and thus eventual deactivation. The iLEM images of hydrother-
mally deactivated catalysts show much lower fluorescence intensity compared to
the fresh FCC catalyst particles, moreover a large fraction of the crystals is damaged
and the large regions of clay are lost.

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2.2.16 Catalytic reactions: product analysis
Various reactors for studying catalytic reactions will be discussed in Chapter 3.

Investigations of catalytic reactions, in addition to providing information on kinetics,
activity, selectivity and deactivation, are also important in the reaction mechanisms.
Detailed product analysis is thus an essential element of each and every catalytic
study. In vary many cases it can be a bottleneck, as although products might not be
unknown their quantification is necessary. Moreover, rapid analysis may be needed.
A brief overview of chromatographic methods is provided here. Chromatography is a
physical method of separation in which the components to be separated are distrib-
uted between two phases, one of which is stationary, while the other moves in a defi-
nite direction. Chromatographic methods are widely used nowadays for analytical
purposes, not only for off-line analysis but also for on-line determination of minute
amounts, as well as large- scale preparative separations. In fact, not only monomers,
but also polymers and oligomers, can be separated by chromatography, although in
the former case it is essentially a group separation. There are several forms of chroma-
tography that use different mobile and stationary phases, with the two main forms of
instrumental chromatography being liquid (LC) and gas chromatography (GC).
2.2.16.1 Gas chromatography

Gas chromatography (GC) (Fig. 2.68) provides qualitative and quantitative determi-
nation of organic components, introduced into the column for separation either di-
rectly or in the derivatized form.
Retention time:
Time for peak maximum
after injection
Injector Detector
Flow
Gas
control
Columns:
Nonpolar (volatility)
Polar (volatility/polarity)
Columns:
Temperature
i.d. = 0.1–0.75 mm
programming
film = 0.1–0.5 μm
1 = 5–50 m
Oven with GC-column
Fig. 2.68: General scheme of GC. Typically the set-up includes also a liquid injector along with an
evaporator.

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Vaporized products passed through the column are identified in a detector,

whose response is recorded as a chromatogram. Thus, in order to be analyzed by
GC, compounds in the samples must be able to get volatilized and additionally pos-
sess thermal stability.
Capillary columns are made of fused silica with a stationary phase as a thin
film of liquid or gum polymer on the inside of the tube. The most common station-
ary phases are siloxane polymer gums with different substituents providing differ-
ent polarities. The polymers are usually cross-linked in the column by photolytic
or free-radical reactions, bringing strength to the polymer films. Wall-coated
open-tubular columns with a liquid-phase coated directly on the inner walls, and
support-coated open-tubular columns are applied. In the latter case a stationary
phase is coated on fine particles, deposited on the inner walls. Among non-polar
columns, those based on dimethyl polysiloxane could be mentioned. HP-5 with
95% dimethyl polysiloxane and 5% phenyl groups is slightly more polar. An even
greater number of polar columns employ polyoxyethylene or polyester liquid-
phases.
Capillary columns are available in a wide range of internal diameters, lengths
and liquid film thicknesses. Although longer columns provide better separation, it
comes at the expense of the analysis time, meaning that this time is increasing,
which is usually not desitrable. In addition, longer columns lead to higher pressure
and thus problems with the injection. Columns with thicker films have higher ca-
pacity, but usually require higher temperature, while thin film columns are suited
for large molecules with low volatility. In principle, the analysis of components
with up to 60 carbon atoms is possible.
Different types of injection systems are used in GC. Split mode, where the in-
jected material after evaporation is split between the column and an outlet, affords
rapid volatilization and homogeneous mixing with the carrier gas. Most of the sam-
ple will pass out through the split vent and only a small proportion will flow into
the column. Splitless systems provide more reliable quantification, allowing analy-
sis of rather high molecular-mass compounds as, for example, triglycerides.
Two types of detectors are mainly applied. Flame ionization detectors (FID) op-
erate in a destructive mode with a current measuring circuit that responds to ions
created by combustion in the flame. These detectors have high sensitivity for hydro-
carbons, but do not detect water. Thermal conductivity detectors (TCD) are non-
destructive measuring changes in conductivity caused by product in the carrier
stream. They are combined with FID.
On-line coupling of capillary columns with mass spectrometers is routine nowa-
days enabling convenient structure identification.
An important issue, which is sometimes forgotten, is that the sensitivity for dif-
ferent compounds is varying for a detector; thus different peak areas are not neces-
sarily in proportion to the weight concentrations. Knowledge of response factors is
therefore necessary and calibration for components should be done properly,

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especially for compounds with various functional groups. Commonly, internal stan-
dard compounds are applied, for example, compounds that are not present in the
sample itself are purposely added. Chemically they should be similar to the sample
compounds with close retention time, however, with no peak overlapping.
What is not that often considered is a necessity to not have any leftovers in the
samples from the previous injections, as heavy compounds, which are difficult to
vaporize, could remain in the GC column and significantly influence subsequent
analyzes. Thus regular control of retention times and response factors, as well as
column cleaning or replacement in due time, should not be overlooked. For some
samples related to the analysis of complex mixtures even pre-fractionation could be
necessary.
In addition to such advantage of GC as accurate quantification based on inter-
nal standards, a possibility to be combined with a mass spectrometer and complete
automation regarding injection and analytical runs, very high resolution should
also be mentioned.
Conversely, only molecules up to about 1,000 mass units can be analyzed, as
they should be stable at high temperatures. Therefore, samples should sometimes
be processed before the analysis and this is important for polar compounds, for ex-
ample, acids, which should be derivatized. GC and GC-MS analysis in the vapor
phase require volatile derivatives that do not adsorb onto the column wall.
Different derivatizations for different substances are recommended and discussed
in the specialized literature on GC.
Recent advanced in gas chromatography are associated with use of multi-
dimensional analysis (two-dimensional or 2D GC). In this version of GC a portion of
the compounds separated on the first column (first dimension) is sent to a second
column (second dimension) for further separation according to different physical
principles. For example, if the first column is apolar with separation through differ-
ent vapor pressure of components mixture, the second column is polar with polar-
ity-based separation. An example of 2 GC is provided in Fig. 2.69.
2.2.16.2 Liquid chromatography

These chromatographic methods use liquids such as water or organic solvents as
the mobile phase. Silica or organic polymers as well as anion-exchange resins are
used as a stationary phase. Separation is performed either at atmospheric pressure
or at a high pressure generated by pumps, which is often called high-performance
liquid chromatography (HPLC) with solvent velocity controlled by high-pressure
pumps, giving a constant flow rate of the solvents. Solvents are used not only as
single solvents but they can also be mixed in programed proportions. In fact, even
gradient elution could be applied with increasing amounts of one solvent added to
another, creating a continuous gradient and allowing sufficiently rapid elution of
all components.

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aro. RCP
OP
aro. R
cis-decalin
RCP
sat.
trans-decalin
sat. ROP
Fig. 2.69: GCxGC chromatogram of tetralin hydroconversion products. Aro- aromatics Sat. saturated;
RCP-ring-contraction products; ROP- ring-opening products. (Reproduced with permission from [34]).
The most commonly used columns contain small silica particles (3–10 μm) coated
with a non-polar monomolecular layer. For low-polar compounds the mobile phase is
an organic solvent, while reversed phase HPLC employs mixtures of water and aceto-
nitrile or water and methanol as eluents and is applied for non-ionized compounds
soluble in polar solvents. UV-Vis and diode-array detectors enabling recording of UV-
vis spectra, or detectors based on refractive index monitoring, are applied.
An important form of HPLC is size-exclusion chromatography (SEC), which is
widely applied for the determination of molecular-mass distributions of oligomers
and polymers. In SEC (Fig. 2.70), solutes in the mobile phase (for example, tetrahy-
drofuran) are separated according to their molecular size. Smaller molecules pene-
trate far into the porous column packing material and thus elute later than larger
ones.
Among the advantages of LC are its non-destructive character and absence of
derivatization. This technique can handle both small and large amounts and it can
also be used for preparative isolation of compounds from mixtures. Contrary to GC
there are almost no, or at least much fewer, limitations in terms of the molecular
size. In addition LC can be combined with mass spectrometry, once again without
derivatization.

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Chromatogram
Time
Fig. 2.70: Size-exclusion chromatography.
Thermally unstable and polar compounds can thus be analyzed as such, and
the molecular mass in triple quadruple or ion-trap LC-MS can be up to 3,000 m/z,
while time- of-flight versions allow up to 16,000.
Although LC-MS provides better sensitivity and selectivity than GC-MS and is
excellent for quantification of selected substances in complex mixtures, this tech-
nique is not very suitable for rapid and reliable identification of unknown com-
pounds, mainly because fragmentation is sparse at mild ionization conditions of
ionization. Moreover, spectra libraries that enable identification are typically not
available. Another shortcoming of LC-MS is the rather low sensitivity of the detec-
tors for certain compounds. Finally, it may be difficult to obtain constant pressure,
which in turn influences retention; clean, degassed solvents are needed and it
might be challenging to find the optimum solvent mixture.
2.2.17 Theory as a part of a toolbox
It is important to emphasize that in catalyst development there is now a close cou-

pling between theory and experiments where the theories are based upon quantum
chemistry and describe single molecular situations. The current level of theory can
be applied simultaneously with experiments, but these experiments cannot yet be
replaced by theoretical calculations. The high sophistication of modern theoretical
concepts requires that chemical engineers if not themselves proficient in theory
closely collaborate with theoretical chemists. Quantum chemical calculations pro-
vide valuable information about adsorption as well as activation energy.
Experimentalists, chemists and chemical engineers should, however, be careful
with interpretation of the modeling results because realistic modeling of technical
catalysts is too complicated and often drastic simplifications are included into
calculations.
Electrons are particles with wavelike properties, therefore, they do not behave
like point-like objects moving along precise trajectories. Instead their trajectory is
replaced by a position-dependent wave function (Ψ ). The basis of quantum chemis-
try is the Schrödinger equation, H ^ Ψ = E Ψ where H is the Hamiltonian for the

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system (an operator containing derivatives), E is the energy of the system. The prob-
ability of finding an electron at any point in space varies with the distance from the
nuclei and is proportional to |Ψ |2.
Solving the Schrödinger equation is challenging because the motion of any
particle is influenced by all other particles and analytic solutions can be obtained
only for very simple systems, such as atoms with one electron. Thus approxima-
tions, being a trade-off between ease of computation and accuracy of the result,
are needed to be able to treat molecules theoretically. For example, a Born-
Oppenheimer simplification for the many-electron Schrödinger equations divides
electrons into valence and inner core electrons. The inner core electrons are
strongly bound and can be excluded from chemical binding calculations, while
valence electrons completely determine binding properties. In such approach an
atom is reduced to an ionic core interacting with the valence electrons, although
the electronic wave function is still a function of the spatial coordinates of the
electrons and their spin variables. Hartree-Fock approximation expresses the
overall wave function as a product of single particle wave functions. This ap-
proach does not include electronic correlations, which account for interactions of
electrons with each other. Additional correlations have been developed to over-
come these shortcomings of the Hartree-Fock approach.
DFT instead of using many-body wave functions uses electron density as the
basic variable. This theory, which became very popular to study many-body prob-
lem, is simpler than the wave function approach and is much less expensive com-
putationally. In this theory, the properties of a many-electron system can be
determined by using functionals, i.e., functions of another function, namely the
spatially dependent electron density. Although DFT provides an exact path to the
determination of the electronic energy of a system in a ground state, and allows
computation of reaction energies and barriers of many complex catalytic systems,
such calculations are computationally very demanding.
An example of DFT calculations [35] is presented in Fig. 2.71 for steam reform-
ing of methane (CH4 + H2O ↔ CO + H2), which will be discussed in detail in
Chapter 4.
These calculations were done for the Ni (111) surface and the Ni (211) surface,
representing a stepped surface. The Ni (211) step sites have lower activation bar-
riers, are more reactive and have more strongly binding intermediates than the
close-packed Ni (111) surface. In addition to pointing out these differences in
activity, DFT calculations were very useful in understanding deactivation by car-
bon formation. It follows from Fig. 2.71 that as carbon is bound stronger at the
stepped surfaces, they could thus be the potential sites of carbon nucleation.
Visualization of the graphene layers growth on step sites by in situ HREM in com-
bination with DFT resulted in a new approach of catalyst promotion by blockage
of the step sites.

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300
H2O 3H2
200 Ni (111)
CH4
E (kJ mol–1)
CO
100
6H
CH3, H CH2, 2H
0 CH, 3H
C, 4H O, C, 6H
Graphene
Ni (211) OH, C, 5H
–100 CO, 6H
Reaction coordinate
Fig. 2.71: DFT calculations for steam reforming of methane. (Reproduced with permission from [36]).
An alternative approach to complete DFT calculations is to develop descriptors

of catalyst reactivity, which will enable design and engineering of more active and
selective catalysts.
Thus for a methanation reaction, which is a reverse of methane steam reform-
ing, i.e., CO + H2 ↔ CH4 + H2O, the group of Norskov [37] demonstrated that the
activity of a certain metal is given by only two descriptors: the C and O adsorption
energies (Fig. 2.72).
The TOF is plotted as a function of carbon and oxygen binding energies for the
stepped 211 surfaces of several transition metals at 573 K, 40 bar H2, 40 bar CO.
The reason for volcano type behavior is that the breaking of the CO bond is
the rate-determining step for relatively unreactive catalysts such as Ni. It proceeds
by bond breaking the OH intermediate, yielding adsorbed C and OH on the sur-
face. On the more reactive metals (Fe) the surface is poisoned by adsorbed carbon
and oxygen because of the faster reaction. A good methanation catalyst thus
should have a reasonably low CO dissociation barrier and reasonably high carbon
and oxygen desorption rates as methane and water. DFT calculations identified
Ni3Fe catalysts as a cheaper alternative with a higher activity than Ni, and this
was verified experimentally.
Further improvements in DFT are needed to treat, among other issues, intermo-
lecular interactions, especially van-der-Waals forces, as well as transition states,
global potential energy surfaces and some other strongly correlated systems, such
as oxides.

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2.3 Preparation of catalytic materials 117
0
Au 2
Ag –1
–1
Pd
Pt –4
Cu
–2
–7
Rh
log (TOF) s–1

Ni
DE 0 (eV)
Ru Co –10
–3
Ni3Fe
Fe –13
–4 –16
Re
–19
–5
–22
–6 –25
–2 –1 0 1 2 3 4
DE C (eV)
Fig. 2.72: Theoretical volcano for the production of methane from syngas, CO, and H2. (Reproduced
with permission from [37]).
2.3 Preparation of catalytic materials
2.3.1 General overview
For many years, the development and preparation of heterogeneous catalysts were
considered to be more alchemy than science. A heterogeneous catalyst is a compos-
ite material, characterized by: (a) varying amounts of different components (active
species, physical and/or chemical promoters, and supports); (b) shape; (c) size; (d)
pore volume and distribution; (e) surface area. The optimum catalyst is the one that
provides the necessary combination of properties (activity, selectivity, lifetime, ease
of regeneration and toxicity) at an acceptable cost.
Although in the past the main determining factors were activity and selectivity
rather than costs of catalysts, nowadays economics and ecological concerns are of
significant importance. The cost/performance ratio sometimes prevents the use of
new technologies for manufacturing catalysts, as they are usually associated with
additional capital investment. Contrary to academic research aimed at the synthesis
of well-defined structures, which could be carefully characterized with the results
published in scientific journals, the industrial approach to catalyst development

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should take into account a number of issues, which are typically of almost no con-
cern in academic research. In addition to activity, selectivity and preparation costs
we should also mention mechanical and thermal properties (resistance to attrition,
hardness and thermal conductivity), morphology and porosity, stability against de-
activation assuring long-term performance, possibility of regeneration and repro-
ducibility of preparation. As many catalysts should be active for a number of years,
industry is also concerned about the ways of predicting the lifetime. To this end,
acceleration tests are performed where catalysts are aged using, for example,
higher temperatures. This might obviously lead to other side processes and not nec-
essarily correspond to the actual lifetime at other process parameters. Catalyst man-
ufacturers are usually concerned about the patent situation and report (if report)
preparation methods as inventions. Judging which methods are used industrially is
very difficult from the patent literature and in the majority of cases the imple-
mented methods are kept as company secrets. The production technologies are not
reported in the engineering literature except for a few processes with rather vague
descriptions.
From my personal experience even catalyst manufacturing companies personnel not involved in
manufacturing can have restricted access to production facilities.
Catalyst scale-up from the laboratory to an industrial scale is not straightforward for
a number of reasons. Typically, the precursors of industrial catalysts are the salts of
catalytically active metals, sols, oxides and natural minerals. The selection of feed-
stock is determined by their constant chemical and phase composition, absence of
undesired impurities, required humidity, costs, etc. Water is another source of impu-
rities, as it is used for dissolution, dilution, washing, etc. Research in academia on
the contrary uses expensive analytical grade reagents, while industry is working with
technical grade substances. Some unit operations are difficult to scale-up, such as
precipitation, which will be discussed below, thermal activation and catalyst forma-
tion in general. Precipitation on a large-scale could even be related with the order in
which compounds are mixed. Taking all this into consideration, catalysts scaling-up
still requires a lot of empirical expertise and knowledge.
Methods for catalysts preparation are very diverse and typically require several
steps.
The most important of these could be identified as: (a) preparation of the pri-
mary solid by precipitation, impregnation, etc.; (b) processing of these primary sol-
ids (thermal treatment, etc.) and (c) activation (reduction, sulfidation, etc.).
Traditionally, catalysts are divided into bulk and supported catalysts.
Bulk catalysts are produced by a number of methods, such as precipitation, co-
precipitation, sol-gel, flame hydrolysis, spreading or melting. Some of these methods
will be discussed in the corresponding sections. For the impregnation supported cat-
alysts the following methods are used: ion exchange, equilibrium adsorption,

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grafting, deposition-precipitation, immobilization of metal clusters, spreading and

wetting, chemical vapor or atomic layer deposition and the anchoring of homoge-
neous catalysts.
2.3.1.1 Preparation of the primary solids

Precipitation and co-precipitation are mainly used for production of oxidic catalysts
and support materials. Two typical examples of such catalysts are iron oxide cata-
lysts for high temperature water-gas shift, and copper oxide-alumina catalyst for
methanol synthesis. Iron oxide catalysts can be prepared by precipitation of iron
carbonate from iron sulfate in the presence of sodium carbonate with subsequent
washing, filtration and calcination.
The mixing and maturation procedures, pH and pH variations could influence
precipitation, which involves nucleation and crystal growth. Nucleation needs
conditions far from equilibrium (supersaturation), while crystal growth finally
approaches equilibrium.
Low supersaturation, which could be achieved under homogeneous precipitation
conditions when the precipitating agent is continuously supplied or produced in situ,
leads to poor dispersion. Although high supersaturation might lead to well-dispersed
catalysts they could thermodynamically be unstable, undergoing Ostwald ripening
(growth of large crystals at the expense of smaller ones).
Catalyst manufacturers typically use water during precipitation, trying to avoid
organic solvents for precipitation because solvent work-up and recycling are expen-
sive. There, are, however, examples when organo-metallic precursors are used in
organic solvents for the synthesis of supports by precipitation. A process for alumi-
num alkoxide production from aluminum metal and an alcohol, was developed by
Condea Chemie. Subsequent hydrolysis also gives an alumina slurry, hydrogen and
alcohol, which is recycled. Aluminosilicates could be produced by the same
technology.
Water could be completely avoided when dry mixing of catalysts precursors is
performed by mechanical activation. During ball milling the particles of easily de-
composable salts (formates, carbonates, oxalates) are crushed and the mechanical
energy is transferred to heat. When heat conductivity is poor, high temperature hot
spots lead to local solid reactions, resulting in catalysts with poor dispersion and
small specific surface area compared those obtained by precipitation. Iron oxide
based catalysts for dehydrogenation of ethylbenzene to styrene are produced by
mechanical activation when potassium hydroxide is put in contact with chromium
and iron oxides.
Gelation methods are based on the continuous transformation of a solution into
a hydrated solid precursor (Fig. 2.73).
The key factors are hydrolysis and condensation rates, as will be discussed later
when the synthesis of silica is described. Initially, hydrophilic colloidal solutions are

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Dissolve a precursor Start with

(metal salt or alk- preformed sols
oxide) in a solvent
Add water and acid

Destabilize sols by Formation
or base for hydro-
abjusting pH
lysis and conden-
or concentration
sation
Formation of a Formation of a gel

self-supporting gel onto a substate
Aging of the gel

Aging
Evaporative Supercritical
drying Drying of the gel drying
for
solvent removal
Solvent
removal
Formation of a Formation of an
xerogel aerogel
Obtaining different
product forms such Heat
as powder, mono- treatment
liths, thin films and Calcinatiory
membranes sintering
Fig. 2.73: Diagram for the different steps in the sol–gel preparation. (Redrawn from [38]).
generated with the micelles separated because of electric charges. Subsequent gela-
tion (Fig. 2.74) depends on the pH, micelle concentration, temperature ionic strength
and temperature. The sol-gel process produces a metastable open-structure polymer
with the units bound by chemical, dipole and van der Waals forces and hydrogen
bonds. The method allows for better control of the texture, composition, structural
properties and homogeneity of the catalysts.
Removal of the solvent should be, however, carefully done, as drying can result
in either aerogels or xerogels, the xerogels being too dense to have an application

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Supercritical
solvent Aerogel
extraction
Xerogel
Evaporation
Heat
Solution (Hydro)gel
of micelles Dense ceramic
Fig. 2.74: Formation of aerogels and xerogels from micelles.
in catalysis. In addition, phase segregation and porosity changes can take place be-
cause of calcinations, thus the sol-gel method is limited to the production of car-
riers such as silica and alumina and to hydrothermal synthesis of zeolites, which
will be discussed in a separate section.
In selective removal one of the components is removed. An example is the prep-
aration of skeletal metals or sponge catalysts such as Raney nickel. Aluminum is
removed from a relatively course powder of an alloy (NiAlx) by leaching with so-
dium hydroxide (Fig. 2.75A). This procedure results in a highly porous nickel cata-
lyst that possesses high activity and, also important for three-phase reactions, a
high settling rate. Sponges are composed of 2–15 nm microcrystallines that have
been agglomerated into macro pores. The surface area of sponge catalysts (which
were and are still used commercially in various hydrogenation reactions such as hy-
drogenation of sugars and oils to margarine), is 50–120 m2 g−1. The catalysts pre-
pared by selective removal have some limitations. Digestion of the less noble metal
Mixing
Melting
Cooling
Crushing
Screening
Exposure to NaOH
(A) solution (pH ca. 14) (B)
Fig. 2.75: Formation of sponge catalysts. (A) General scheme, (B) Storage of catalysts.

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from a bimetallic or polymetallic alloy results in highly pyrophoric catalyst, which

starts to burn spontaneously in air when dried and should be thus kept and trans-
ported under water (Fig. 2.75B). Difficulty in process control also means challenges
in the reproducibility of the preparation. In addition, the overall costs are high be-
cause of the high-energy consumption needed for melting.
In supported catalysts catalytically active compounds are attached to a support
with a large specific surface area. The preparation of these catalysts includes depo-
sition of the precursor on the support surface and transformation of the precursor
in the required active phase (metal, oxide, sulfide). The precursor type and concen-
tration, nature of the support, presence of promoters, and conditions of the prepa-
ration influence chemical interactions of the precursor as well as the final active
phase interactions, with the support being decisive for the performance of the cata-
lyst in terms of activity and selectivity.
Impregnation is one of the methods of depositing the active phase on a support
and could be performed by contacting a certain volume of solution with a precursor
and the support (Fig. 2.76).
Support,
often porous grains
Dipping Impregnated Active

support catalyst
Drying Reduction
Metal salt Calcination
solution
(A)
Desorption
Adsorption Evaporation
Adsorption
Solution flow Adsorption/desorption Drying

(B) into pores + diffusion
Fig. 2.76: Impregnation of supports. (A) The overall process and (B) processes in a pore.
In wet impregnation an excess of solution is used, which is eliminated by evapora-

tion or draining. Deposition is slow and can take hours or even days, therefore, there
is an apparent danger of surface restructuring. Moreover, quantitative deposition of
the precursor is difficult to achieve. In pore volume impregnation the volume of the

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solution containing the precursor corresponds to the volume of the pores. A similar
method is incipient wetness impregnation, the difference being that the volume of
the solution is more empirically determined for the catalyst to start looking wet.
For both methods the operating variable is the temperature, which influences
both the precursor solubility and the solution viscosity and as a consequence the
wetting time. The concentration profile of the impregnated compound depends on
the mass transfer conditions within the pores during impregnation and drying.
The maximum loading in these methods is limited to the solubility of the pre-
cursor in the solution. Several active components could be introduced in successive
impregnations with drying and even calcinations between these impregnations.
Ion exchange is based on replacing an ion in electrostatic contact with the sup-
port by another ion. The latter ions gradually penetrate into the pore space of the
support, while ions initially present in the catalyst pass into the solution until equi-
librium is established, corresponding to a certain distribution of the two ions be-
tween the solid and the solution. In synthesis of zeolites for example, a sodium ion
is replaced by ammonium during ion exchange, followed by the subsequent calci-
nation and finally resulting in proton forms of zeolites.
Anchoring of a precursor from an aqueous solution can be done by adsorption
(Fig. 2.77), which occurs on charged surfaces, as frequently used supports like
metal oxides and active carbons develop a pH-dependent surface charge. The metal
precursor should thus be selected based on the surface charge, which depends on
the isoelectric point of the oxide (pH at which the surface is neutral), pH and solu-
tion ionic strength.
Support
adsorbed
Amount
Drying
and firing
Concentration
Fig. 2.77: Adsorption.
Precipitation onto the support surface (deposition-precipitation), which requires

lower supersaturation than in bulk precipitation, should be carefully performed to
avoid precipitation in the solution bulk (Fig. 2.78). A well-dispersed and homoge-
neous active phase is reached when the OH– groups of the support interact directly
with the ions present in the solution. A constant level of supersaturation is then

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Change of T, pH
or concentration
Decrease solubility of metal

Metal salt solution
Fig. 2.78: Precipitation.
achieved, for example, by decomposing a suitable substance that releases the pre-
cipitation agent (OH–) continuously, as in the case of urea hydrolysis. Precipitation
with urea starts with dissolving it in water and its decomposition slowly at ~90 °C,
giving a uniform concentration of OH– in both the bulk and pore solutions. Thus
the precipitation occurs evenly over the support surface, making the use of urea the
preferred method for amounts higher than 10–20%. Another option is to have a
controlled and progressive addition of this precipitation agent. The use of porous
supports might lead, however, to deposition-precipitation at the external surface.
A particularly interesting example in this respect is preparation of nanosized gold
particles, which are very different catalysts from “bulk gold” in terms of their reactiv-
ity. The deposition precipitation method using urea was reported by Fokin already in
1913 [39] without certainly measuring the size of gold deposited on asbestos (!) and
utilized in oxidative dehydrogenation of methanol to formaldehyde. In fact, gold on
this support was even more active than supported silver, although utilization of sup-
ported silver catalysts became an industrial reality. This paper of Fokin written in
Russian language remained in oblivion even if it was cited in a textbook of Sabatier
published few years after the original discovery. Tremendous interest in catalysis by
gold is mainly due to much later work of Haruta and Hutching. The latter scientist
while working in industry found that gold was the best catalyst for acetylene hydro-
chlorination giving vinyl chloride monomer. Currently, carbon-supported mercury
chloride is used commercially. For example, only in China approximately 13 million
tons per year are produced in more than 90 plants with up to 100 reactors per plant
having each of about 6–7 tons of catalyst per reactor. From the overall capacity of
15,000 tons, approximately 1,000 tons per year are simply lost because HgCl2 is vola-
tile. There are currently efforts to replace this catalyst with 0.1% Au/C extrudates, re-
sulting in essentially the same productivity.
Monolithic catalysts are produced by two main methods. In the first, catalytic
compounds are incorporated into the monolith before formation of the monolithic
structure. A significant amount of the active compound is not accessible because of
a long diffusion path. Deposition of the active phase directly on the monolith is
also possible. As ceramic monoliths have low surface area wash-coating is an alter-
native way of active phase incorporation. This consists of depositing a layer of a

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high surface oxide, carbon or polymer onto the surface of a low surface area mono-
lith. Introduction of the active phase is done either during wash-coating or after it
by methods already presented above, such as impregnation, ion exchange, precipi-
tation, deposition-precipitation. Specific methods could be also applied, such as
thermal spraying, spin coating or chemical vapor deposition (CVD). CVD is an ex-
ample of a gas deposition method, where deposition is done by adsorption or reac-
tion from the gas-phase. Another popular method is atomic layer deposition, which
will be discussed in detail later. These methods of gas deposition result in catalysts
with controlled metal dispersion, which could be very high at significant loadings.
2.3.1.2 Treatment of intermediate solids or precursors

Treatment of intermediate solids includes filtration, washing, drying, thermal de-
composition, calcinations and activation. Activation could also be done after form-
ing the catalyst (methods briefly mentioned in Section 2.3.1.3 and described in
further detail in Section 2.3.7).
In the case of cake filtration (Fig. 2.79), a relatively thin filter medium is used and
separation is achieved on the upstream side of the medium. The particles should be
either larger than the pores of the medium or should form bridges to cover the pores.
A cake is formed from successive layers of solid deposits apparently increasing the
pressure drop for the case of dead-end filtration.
Feed
Permeate Fig. 2.79: Schematics of dead-end cake filtration [40].
An increase in the cake height during deposition of solids apparently results in an

increase in the total cake resistance. In an incompressible cake with a linear in-
crease of resistance with height, the filter cake porosity remains constant while the
cake volume increases. Filtering at constant pressure as implemented in vacuum
filtration results in decline of filtration rates as the filter cake is growing in size. Too
thick filter cakes lead to prolong filter cycles because of low filtering, dewatering
and washing rates. Steps in a filtering cycle include besides filtration per se also

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dewatering, washing, filter cake discharge, cleaning, reassembly and filling of the
filter.
In continuous large-scale vacuum filters, the suspension is introduced to the
filter at atmospheric pressure. Vacuum applied on the filtrate side of the medium
creates the driving force for filtration. The rotary vacuum drum filter is illustrated in
Fig. 2.80.
Washing water
Dew
ate
cake rin
g
on
zo
cti
ne
su
suc so
tion lid
pro
du
central ct
ion duct
suct
knife
on
suct
cti
su
on i
Filtration zone
Fig. 2.80: Schematic of a rotating vacuum filter [41].
As the drum rotates, being partially submerged in the slurry, solids trapped on the
drum surface are washed and dried. The cake discharge occurs at the end of the
rotational cycle. The drum surface covered with a cloth filter medium can be pre-
coated with a filter aid to improve filtration and increase cake permeability.
Horizontal filters such as the horizontal belt filter presented in Fig. 2.81 allow
settling by gravity before the vacuum is applied. Horizontal belt filters having a sim-
ple design and low maintenance costs have difficulties to handle very fast filtering
materials on a large scale.
The filters described earlier operate in a continuous mode. Nutsche filters,
which are basically vessels divided into two compartments with vacuum applied
to the lower compartment, can operate batch-wise. This might be necessary in
case of stringent washing requirements or if there is a need to keep batches sep-
arated. The Nutsche (Fig. 2.82) filters can handle batches of 25 m3 and a cake
volume of 10 m3 and are able thus to work with an entire charge of slurry.
Sufficient holding volume is required for fast charging and emptying of the ves-
sel. The difficulties of operation with such filters arise when cakes are slow to
form, sticky and the product deteriorates during long downtime. The operational

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Filter cloth
Slurry feed device Cake washing device Cloth drive roller
Vacuum tray drive
Cloth tension device

Cloth tracking device
Cloth washing
device
Vacuum pump
Fig. 2.81: Schematic of a horizontal belt filter [42].
Pressure
Filtration
drying
Cake Vacuum
washing drying
Cake
Repulping discharge
Fig. 2.82: Nutsche filter: (a) Photo [43] and (b) schematics of operation [44].
sequence starts with filtration per se when the filter is charged with slurry and
the pressure is applied. In the washing stage, the wash liquid is introduced over
the cake displacing the mother liquor. In the drying stage, air or gas purges the
cake until the desired drying level. The final step is the cake discharge and in
some instances washing the cloth or woven mesh screen with water to remove
any cake residue.
Washing is essentially a replacement of the mother liqueur with pure water,
with desorption or exchange of certain undesirable ions for those that could be

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decomposable during calcinations. Thus, for example, a known catalyst poison like
Cl– is washed away by water or replaced with NO3− .
Drying, which is the elimination of the solvent (usually water) from the pores of
a solid, is done at temperatures higher than critical temperature of water or by evapo-
ration under vacuum at low temperatures (from −50 °C to −5 °C). Inappropriate dry-
ing can result in non-uniform distribution along the catalyst grain of an active
component not strongly bound to the surface. Slow drying or freeze drying can be
used to avoid such problems. Drying of powders with the channels above 10 μm is
faster than for smaller ones. The drying rate depends on the catalyst shape being
faster for spherical particles than for cylindrical ones.
The objective of calcinations is to develop a well-defined structure for the active
agents/supports, modify the support structure by, for example, transforming γ-
alumina to α-alumina, adjust the texture and pore volume and to provide mechani-
cal resistance.
Calcination means heating without the formation of a liquid-phase and is a fur-
ther heat treatment beyond drying. It can determine the properties of the final cata-
lyst, as many processes are occurring, such as decomposition of the precursor,
spreading, sintering, and formation of new phases from the active material and the
support. Calcination is specific for each system and depends on the gas-phase.
Although air is often used, inert gases or controlled water vapor atmosphere could
be also applied.
Typically, however, calcination is carried out in air at temperatures higher than
those used in the catalytic reaction or catalyst regeneration.
In a chain-like belt, calciner gases can circulate readily through the belt and
the catalyst of a fairly larger size in the form of extrudates or pellets. Because for
catalyst shaping, lubricants are added to aid extrusion, they are burned out during
calcination, which might lead to excessive temperature increase. A remedy in such
cases is to limit the oxygen content or alternatively to perform calcination in a tem-
perature-programmed mode to control oxidation of combustible materials present
in the catalyst.
The word “calcination” is used because of historical reasons, as burning of cal-
cium carbonate (limestone) to calcium oxide (quick lime) proceeds with removal of
CO2 (i.e., a process obviously beyond drying). A limestone calciner (rotary kiln) is
shown in Fig. 2.83.
Apart from loss of chemically bonded H2O or CO2 several other processes occur
during calcination or heating, such as modification of the nature and/or structure of
the phases present, generation of the active phase and stabilization of mechanical
properties and texture modification through sintering. The heating temperature and
atmosphere must be properly chosen to obtain phases that are stable in the reaction
and regeneration conditions, at the same time avoiding excessive sintering phenom-
ena (agglomeration of crystals) as much as possible, as they have a negative effect on
the catalytic performance. In order to understand at which temperature sintering can

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Fig. 2.83: Panoramic view of rotary kiln (photos of the author).
occur for a particular metal it is important to know the Tamman temperature TT and
Hüttig temperature TH when lattice and surface atoms, respectively, become mobile.
Semi-empirical relations between these temperatures and the melting temperature
Tmelt
TT = 0.5 Tmelt , TH = 0.3Tmelt (2:23)
where T (K), indicate that when the melting temperature is not as high as for some
metals (Cu: 1,357 K, Ag: 1,234 K) sintering can be profound at temperatures typically
used for the thermal treatment of catalysts.
Technical arrangements of drying, calcination and activation should be per-
formed in a way that all the catalyst particles are exposed to the same conditions,
which is not possible to achieve in fixed beds. One should also realize that condi-
tions of these treatments and applied equipment in the lab and industrial scales are
very different. For example, different types of moving beds are used in industry
(Fig. 2.84).
Activation refers to other thermal treatments, such as reduction of metal sup-
ported catalysts or sulfidation of hydrodesulfurization catalysts, usually performed
in special atmospheres in the reactor at the start-up of the unit. Therefore, activa-
tion is not considered strictly to be a preparation procedure. Reduction is mostly
done with hydrogen and a higher dispersion is obtained with a higher reduction
rate unless nucleation is a limiting factor. Some catalyst manufactures do not have
hydrogen at their production facilities and use chemical reductants like formic
acid. It should be noted that reducibility of supported metals might be different to
bulk materials and the preparation of bimetallic catalysts could be complicated be-
cause of a possible preferential reduction of one metal before the other. In Fig. 2.85
hexachloroplatinate is used as an example of the complexity of calcinations and
the reduction processes.

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Fig. 2.84: Calcination. (From [45].)
[Pt(C4H7)2]s Ptdisp
300 °C
110 °C
OH
HCO
300
ion
uct 0°
C α-[PtO2]s
C
red 26
°C
0°
itu
In s
29
+ 0 °C
60
0
50
CH
°C
300 °C 500 °C
[PtIVCl6]s2– [PtIV(OH)x Cly]s [PtIVOx Cly]s β-[PtO2]s
C
70 C
60 CH
0°
0°
0°
60
+
O2
H2 Ptcryst
Fig. 2.85: Effect of pre-treatment on Pt/alumina.
Because of the presence of catalyst particles in technical catalysts with different

location depth, crystalline size, interaction strength with the support, etc., activa-
tion rate is usually diminished as the process proceeds and some catalytic species
might not be properly activated. The degree of activation (for example, degree of
metal reduction) should be examined, which might not be easy when such reduc-
tion is done at a plant site in a catalytic reactor.

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2.3.1.3 Forming
When a powder in a water suspension is fed through a nozzle that is spraying small
droplets into hot air, such spray-drying process results in 10–100 μm particles of an
almost identical shape. They could, in principle, be used in fluidized bed reactors.
As discussed in Chapter 1 such small particles result in large pressure drops when
applied in fixed beds, therefore forming operations are required.
Granulation of humidified powder could be performed in a horizontal rotating
cylinder or a pan rotating around a 45° axis. Prior to this the powder is crushed,
ground (in the presence or absence of a liquid, typically water) and screened. In
granulation, different-sized particles are put into motion with a spray of liquid, re-
sulting in particles of 1–20 mm with a broad size distribution and high-pressure
drop. The slurry might contain binders for better adhesion and layer-by-layer
growth of particles that are predominantly spherical after granulation.
Extrusion is the most economic and commonly applied shaping technique for
catalysts and supports. During extrusion a wet paste from a hopper at the top is
forced through a die and the emerging ribbon that passes through holes in the die
plate is cut to the desired length using a suitable device (Fig. 2.86).
Slurry
Die plate
Extrudate
Fig. 2.86: Principle of extrusion.
Usually the catalyst powders obtained after the thermal treatments behave like
sand, i.e., do not have by themselves the required moldability and plasticity, even
when water is added. Various additives are used in the formulation of pastes,
such as: (a) compounds for improving the rheological behavior (clays or starch);
(b) binders (alumina or clays); (c) peptizing agents to de-agglomerate the particles
(dilute acetic or nitric acid); and (d) combustible materials to increase the porosity
(carbon black, starch, etc.).
The operating variables include mixing time, additive content, water content,
aging and extrusion temperature. The quality of the extrudates also depends on the
drying and calcination procedure. Special shapes (trilobates, rings, hollow cylinders,

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monoliths or honeycombs) can be obtained using proper dies. Press extrudates for
viscous pastes and screw extrudates for less viscous ones are mainly used.
Pellets or tablets of few a mm are obtained by dry tableting, which is more
expensive than extrusion. A dry powder is pressed between two punches in a
press with a pressure up to 30 MPa. Small cylinders and rings are formed because
of this compression. Plasticizing agents, such as graphite, stearic acid or talc,
binders (alumina, clays) or porosity additives (i.e., polymer fibers) could be added
during tableting to achieve the desired properties.
More details on the forming methods will be given in Section 2.3.7.
2.3.2 Unsupported metals
2.3.2.1 Colloidal catalysts

Synthesis of metal blacks can be done by reduction of aqueous solutions of their
salts with hydrogen, formaldehyde formic acid and hydrazine. This procedure re-
sults in large metal particles having a surface composed mainly of face atoms.
Polymer stabilized metal nanoparticles do not undergo coalescence and agglomera-
tion (Fig. 2.87).
Repulsion
Metal
Stabilizer layer nano-
Metal particle
nano-
particle
Fig. 2.87: Principles of nanodispersed metal nanoparticles.
Metal precursors, surfactants, solvents and reducing agents are needed for the syn-
thesis of nanoparticles by colloidal methods. Typically, chlorides, nitrates, sulfates,
and acetates are selected as metal salts. Moreover, two or more precursors can be
applied to generate bimetallic nanoparticles.
Nanoparticles can be prepared, for example, by microemulsion methods.
Microemulsion is a system containing water, oil and a surfactant, with the dis-
persed phase having monodispersed droplets of the size 5–100 nm. The size of
water droplets in a continuous oil phase for water-in-oil microemulsions, surfactant
concentration and the nature of the precipitation agent are the parameters regulat-
ing the properties of nanoparticles. Nanocolloids can be synthesized by mixing

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microemulsions containing the metal precursor and the precipitating agent or the
reducing agent. Alternatively, the precipitating agent can be added directly into the
microemulsion containing the metal precursor. Surfactants, such as various organic
molecules and polymers, ensure colloidal stability of nanoparticles. The variations
of the precursor, reductant, surfactants, additives and conditioning are used to con-
trol the shape and size of the nanoparticles. Cationic or anionic surfactants can be
applied. Cationic cetyltrimethylammonium bromide or chloride is used together
with n-hexanol as a co-surfactant. Water-to-surfactant ratio is a parameter that con-
trols the size of particles, for example, larger particles are formed when this ratio is
higher.
Poly (N-vinyl-2-pyrrolidone) (PVP) is one of the polymers that is used effi-
ciently to control the size of transition metal nanoclusters by varying its concen-
tration: larger concentration leads to smaller nanoclusters. Polyvinylalcohol
(PVA) is used for synthesis of gold nanoparticles, which could be thereafter de-
posited on a required support. This method is particularly useful in synthesis of
gold catalysts supported on carbon, when other preparation methods result in
poor metal dispersion.
Formation of nanoparticles can be explained by simple nucleation and growth.
Prior to nucleation, in a super saturation step the concentration of monomers in-
creases up to a point of spontaneous generation of clusters. This results in a decline
of monomer concentrations, preventing nucleation of new particles. The particles
that are available in the solution start to grow. As growth can also occur during the
nucleation phase, short nucleation phases and slow growth kinetics are required,
to allow for narrow cluster size distribution.
The most favored shape with a minimum surface area and an interfacial free
energy for an fcc structure of metal nanoparticles is truncated octahedron. By intro-
ducing special additives it is possible to achieve not only the size but also shape
control. This is because of the different affinity of surfactants to different crystal
facets hindering growth of a facet with preferential surfactant binding. The shape
of Pt nanoparticles could be changed by varying the concentration of the surfac-
tants and through a control of reduction kinetics (Fig. 2.88).
One of the challenges in the colloidal preparation method is the removal of sur-
face capping molecules that could deteriorate catalytic activity. Determination of
metal cluster size (metal dispersion) by TEM and probe gas chemisorption can thus
give very different values. This is then reflected in potentially erroneous calcula-
tions of TOF. Stability of nanoparticles at high temperatures against sintering
should be also ensured. The size of particles could also change during a catalytic
reaction because of Ostwald ripening.
The shape purity of resulting nanoparticles still needs to be improved. In addi-
tion the size of particles is often rather large, exceeding 10–20 nm with conse-
quently low efficiency. Moreover, the stability of shape-controlled nanocatalysts
during the reduction and prevention of leaching are unresolved issues. New

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1. PVP
1. TTABr 2. NaBH4
2. NaBH4 3. H2
1. TTABr
2. NaBH4
3. H2
Fig. 2.88: Schematics illustrate a generic synthetic procedure for preparing Pt nanoparticles
with cube, octahedron and cuboctahedron shapes (TTABr, tetradecylammonium bromide; PVP,
poly-vinylpyrrolidone. (Reproduced with permission from [46]).
developments in the application of colloidal methods in catalyst preparation are

related to the formation of core-shell, hollow and multi-branched (dendrimatic)
mono, bi- and multi-metal nanoparticles. More details on the synthesis of precious
metal nanoparticles are provided in the review by Jin [47].
2.3.2.2 Bulk metal catalysts

Only a few catalysts belong to this group of unsupported bulk metal catalysts.
Synthesis of sponge catalysts has been briefly addressed before. Another important
example is an iron catalyst for ammonia synthesis (Fig. 2.89). Melting of iron ore in
an electric furnace occurs at 1,600 °C and during this process promoters such as
alumina and silica are introduced into the furnace, while other promoters (CaO and
KNO3 or K2CO3) are added in the subsequent chill cast step in a shallow tray when
oxygen is fed at 1,600–2,000 °C.
The melt is first cooled down and then the catalyst is crushed, separated from
the undersized particles and screened. Oversized particles are further crushed,
while smaller than required particles are recycled to the casting stage or melted in
another furnace at 1,600–1,800 °C. This melt is cooled, then crushed and sieved
into several size fractions (for example, 6–10 mm; 1.5–3.0 mm, etc.) depending on
the operation requirements. The irregular granules of iron catalysts are formed
using this method when the melt is passed through a hole and is put in contact
with a cooling liquid. The catalyst mix crystallizes rapidly when cooled below a
temperature of 570 °C to form a solid solution of wustite and alumina in the magne-
tite crystal lattice with a rather small surface area (1–2 m2 g−1).

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3 10
2 Fe
4
O2
11
1 8 12
7
8
9
5
6
13
Fig. 2.89: Scheme for iron oxide synthesis, 1, screen; 2, drum; 3, lift; 4, furnace; 5, feeder; 6,
crushing; 7, oxidation; 8, cooling; 9, bunker; 10, cyclone; 11, bunker of undersized fines; 12,
furnace; 13, storage of catalyst. (Redrawn from [48]).
In general, parameters such as holding time, gas phase nature, efficiency of

mechanical mixing and homogeneity of temperature in the melt are important to
achieve homogeneity of the melt composition. For alloy catalysts, the final compo-
sition is also controlled during cooling the melt by regulating the rate of cooling,
crystallization kinetics and uniformity of temperature across the bulk of the melt.
Slow cooling results in the thermodynamic equilibrium composition, while rapid
cooling (> 100 K/s) gives metastable amorphous, glassy phases. The latter can be
transformed into nanocrystalline materials, which may be also metastable in com-
position and catalytically active. Such metastability is desired for fused iron oxide
catalysts where unique crystallographic states cannot be prepared by the precipita-
tion method followed by calcination. Rapid cooling also influences the formation of
smaller crystallites.
2.3.3 Preparation of bulk oxides by precipitation
Precipitation of metal salts or hydroxides is a widespread method to produce bulk

oxides allowing for more uniform mixing and uniform distribution of active species.
Methanol and Fischer-Tropsch syntheses catalysts are examples of catalysts pre-
pared by precipitation. This method gives more control over pore size and pore size
distribution as it is not limited to the formation of a support. Thus, catalysts of dif-
ferent size and shape could be prepared. Nitrates are usually the preferred precur-
sors because of their high solubility in water, availability and comparatively low

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price. However, careful control of NOx emissions is required. Other salts, such as
sulfates and chlorides could be also applied, although their disposal could be chal-
lenging. As mentioned above, in special cases in industry more expensive organic
compounds are used for the manufacturing of supports. In addition to mixing com-
ponents well on an atomic scale, precipitation can afford high loadings at relatively
high dispersion. At the same time, low loadings give low dispersion.
Despite the apparent superficial simplicity of the method, a number of parame-
ters (Fig. 2.90) influence the quality of the final product, therefore even if the chem-
ical composition of a particular catalyst could be the same for several industrial
manufacturers, properties could be still very different.
Solvent Mixing
sequence
Supersaturation
Textural Temperature
properties; Precipitate
Particle size; composition;
rate of crystallinity Phase;
homogeneity
precipitation textural
properties
Precipitating Phase; Precipitate Textural

agent homogeneity Additives
properties
Purity;
Morphology; Phase; crystallinity;
textural Phase purity; textural
properties precipitate properties
composition
Anion pH Aging
Solution
composition
Fig. 2.90: Parameters influencing precipitation. (Reproduced with permission from [38]).
Synthesis complexity also explains why the scaling up of precipitation is difficult.

For the methanol synthesis Cu/ZnO catalyst, changing precipitation conditions
many result in different phases with varying catalytic activity. The precipitation
method requires large consumption of chemicals and gives high amounts of process
water.
For easily soluble compounds a classical theory of crystallization from oversa-
turated solutions can be applied in order to understand the mechanism of precipita-
tion. After forming a supersaturated solution precipitation is initiated by physical
or chemical means, resulting in nucleation followed by the crystal growth. The

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precipitate formed after aging and modification undergoes spray-drying or is first

filtered and then dried. The dried material is further calcined and then shaped.
These operations could be also performed in the reverse order.
The processes occurring during precipitation are shown in Fig. 2.91.
Precipitate
Metal ion
Concentrations
Nucleation
regime
Nucleation threshold
Equilibrium
Precursor
concentration
Time
Fig. 2.91: Dependence of concentration on time during precipitation.
During dissolution of a salt the following processes occur:

m +
Mem + + nH2 O ! MeðH2 OÞn
m + h im − p
MeðH2 OÞn + pH2 O ! MeðH2 OÞn − p ðOHÞ + pH3 O +
Hydrolysis products are polymerized into complexes of [Me(OH)m]np+ type, where n

depends on hydrolysis conditions and the nature of the metal. Intensive mixing im-
proves the rate of dissolution. Another important parameter is temperature. For
most substrates, such as chlorites, nitrates, ammonium salts, solubility in water im-
proves with temperature increases. However, several salts, such as sodium sulfates
and carbonates display maximum solubility as a function of temperature.
Precipitation, happening after dissolution of the precursors, consists of nucle-
ation and crystal growth. The catalytically active phase is typically metastable, thus
crystallization, which is enhanced at low temperatures, should be performed at
conditions far from equilibrium.
In general, kinetics of solid–solid phase transformations tends to be much
more slower than liquid–solid transformations because of higher activation en-
ergy related, among other reasons, to larger solid–solid interfacial energies,
smaller changes of free energy per unit volume and slower solid-state diffusion.
As a consequence, solid–solid phase transformations rarely reach equilibrium,

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resulting in the formation of metastable phases as mentioned earlier. Nucleation

and growth depend not only on temperature and supersaturation, but also on
impurities.
Supersaturation must first be achieved independent of from which phase crys-
tals can be grown. The degree of supersaturation is expressed by the concentration
difference Δc:
Δc = c − c* (2:24)
where c is the actual solution concentration and c* the equilibrium saturation

value. The supersaturation ratio S defined as
S = c=c* (2:25)
is commonly used in explaining crystallization.

The fundamental dimensionless driving force for crystallization is expressed
through the chemical potential difference of a given substance in the transferring
(solution) and the transferred (solid) states
Δμ=RT = lnða=a*Þ = ln S (2:26)
where a* is the activity of a saturated solution, implying that
S = expðΔμ=RTÞ (2:27)
Solubility–supersolubility diagram (Fig. 2.92) is often used to illustrate how concen-

tration depends on temperature.
Concentration
Supersolubility
curve Solubility
curve
Spontaneous
nucleation Supersaturatd
solution
MSZW
Unsaturated
solution
Temperature
Fig. 2.92: Solubility–supersolubility diagram with MSZW denoting the metastable zone width.
While position of the lower equilibrium solubility curve can be accurately deter-
mined, location of the upper supersolubility curve is less clear as it is influenced by

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many factors such as the rate of supersaturation, agitation intensity, presence of

crystals or impurities. The metastable zone width visible in Fig. 2.92 is thus charac-
teristic of a particular crystallization system.
Nucleation may occur by means of homogeneous or heterogeneous mecha-
nisms, either through primary (absence) or secondary route (presence of crystals).
In primary homogeneous nucleation, nuclei are generated from the solution, while
for heterogeneous nucleation, the solid surfaces are involved.
For homogeneous nucleation, the most likely shapes are spheres as this shape
minimizes the amount of interfacial area per unit volume. The total Gibbs energy
change, ΔGtot, involved in forming a spherical nucleus of radius r is defined
through
4 3
ΔGtot = ΔGvolume + ΔGint = πr ΔGV + 4πr2 γ (2:28)
3
where ΔGV is the free energy per unit volume released upon creating the
new second-phase particle. This term is negative to allow a phase transition. The
interfacial energy per unit area γ is positive as energy is expanded when an inter-
face is created. This term is associated with the creation of new interfacial area.
The total free energy change caused by agglomeration can be expressed as a
function of the nuclei number (Fig. 2.93).
ΔG ΔG
a
ΔG*
ΔG* b
0 0
n* n r* r
c
(A) (B)
Fig. 2.93: Dependence of Gibbs energy as a function of nuclei precursors: (A) amount and
(B) radius.
Fig. 2.93(A) demonstrates the influence of nuclei number on Gibbs energy, which is
composed of the difference in free energy between the solution and bulk species,
free energy change related to formation of the interface as in eq. (2.28) and other
changes, for example, because of strain or the presence of impurities. Obviously,
for agglomeration to occur the Gibbs energy should be negative, which happens
when the critical number of nuclei is reached. This number n* depends on the su-
persaturation ratio S. Without saturation (case a in Fig. 2.93A) nuclei are not

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formed. For higher supersaturation (compare cases b and c in Fig. 2.93A) there are
more nuclei with a smaller size, resulting at the end in a precipitate with a smaller
size. Therefore, in order to increase the number of nuclei, concentrated solutions of
precursors should be used.
An important concept in crystallization is the critical crystal size r* (0.5–5 nm)
illustrated in Fig. 2.93B, starting from which there is a fast growth of nuclei result-
ing in a large number of crystals of different sizes. For lower r* the degree of su-
persaturation should be higher. Beyond the critical nucleus size r*, the total free
energy of the system is decreasing and it is energetically unfavorable for nuclei
to continue growing, while above the critical size (r > r*), there is a continuation
in growth.
The critical nucleus size r* can be determined by taking the derivative of eq. (2.28)
and setting it equal to zero
∂ΔGtot ∂4πr3 ∂4πr2

=0= 3 ΔGV + γ = 4πðr*Þ2 ΔGV + 8πr*γ (2:29)
∂r ∂r ∂r
Giving
r* = − 2γ=ΔGV (2:30)
When nucleation occurs heterogeneously at specific sites (surfaces, interfaces or

grain boundaries), the total free energy associated with the nucleating phase is
4 3
ΔGtot = ΔGvolume + ΔGint = πr ΔGV f ðθÞ + 4πr2 γf ðθÞ (2:31)
3
which is different from homogeneous nucleation by a factor f(θ), accounting for ge-
ometry of the cap compared to a sphere.
*
The critical nucleus size rhet for heterogeneous nucleation calculated in a simi-
lar fashion as for homogeneous nucleation, that is, setting ∂ΔGtot =∂r = 0, gives the
*
same expression rhet = − 2γ=ΔGV as for homogeneous nucleation (i.e., eq. (2.30)).
For heterogeneous nucleation, activation barrier, ΔG*het, is different from ho-
mogeneous nucleation and is defined as
4
πðr*Þ3 ΔGV f ðθÞ + 4πðr*Þ2 γf ðθÞ =
ΔGtot = ΔGvolume + ΔGint =
3
(2:32)
4 2γ 3 2γ 2 16πγ3
= π − ΔGV f ðθÞ + 4π − γf ðθÞ = f ðθÞ
3 ΔGV ΔGV 3ðΔGV Þ2
Concentration of nuclei (n*) that can be formed at any given temperature T is calcu-
lated through the change in ΔG*:

n*het = n0 exp − NA ΔG*het =RT (2:33)

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BecauseΔG*het strongly decreases with decreasing θ, n*het increases exponentially

with decreasing θ explaining why concentration of viable heterogeneous nuclei is
orders of magnitude higher than the corresponding value for homogeneous nuclei.
The size of the critical nuclei is often expressed through the Gibbs-Kelvin equa-
tion [49]:
* 31
* 3n v 2γv
r = = (2:34)
4π kT ln S
where n is the number of precursor species, v is the molecular volume of precursor,

γ is the interfacial energy, and S is the supersaturation ratio.
From eq. (2.35) it can be concluded that the size of the critical nuclei depends
on ln S. It is, however, difficult to control nucleation by alteration of the supersatu-
ration ratio. A more efficient way is through the interfacial energy (surface tension).
The size of the nuclei is smaller for higher supersaturation and smaller surface
tension (interfacial energy), and the latter could be affected by solution pH, ionic
strength through changing nature and the concentration of electrolytes or adsorp-
tion of ions.
The size distribution of the particles depends on the duration of the nucleation
period; shorter nucleation results in more monodispersed particles, while if the nu-
cleation period is long a wide particle size distribution is obtained.
Although nucleation is decisive, growth, limited by surface reactions, is also
important because the crystal size depends on the ratio of rates rnucleatjon and
rgrowth. In most crystal growth processes, not only diffusion but also surface re-
actions are important. As a result, the crystal growth kinetics often depends not
only on the crystal size but also on the surface structure. The growth rate can
be represented with the first-order kinetics in the solute concentration, while
the nucleation rate is defined as proportional to the supersaturation concentra-
tion and the number of critical nuclei, corresponding to supersaturation.
Rapid precipitation can be initiated by adding seeds to the solution increasing
the concentration of the solution at the interface. High stirring favors formation of
small crystals, because the concentration at the interface is increasing, while higher
temperature increases the crystal size.
Crystallization is complicated by the so-called Ostwald ripening. Solubility of
small crystals is higher than of the larger particles. Concentration in the solution in
equilibrium with a solid particle depends on the particle size. The larger the particle
the lower the equilibrium concentration, thus particles larger than equilibrium size
will grow, while for particles smaller than the equilibrium size at a certain concen-
tration the solution is not saturated and the particles dissolve. Thus, during precipi-
tation in addition to nucleation and crystal growth larger crystals are also formed at
the expense of the smaller ones.

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Nucleation and growth are not separated in time as once few viable nuclei are
formed they start to grow. The Johnson–Mehl equation describes the overall trans-
formation rate:

. :
FðtÞ = 1 − exp − ðπ=3Þ N G3 t4 (2:35)
Relating the overall fraction of the transformed material as a function of time [F(t)]
with the nucleation (Ṅ) and the growth (Ġ) rate considered to be time independent.
The third power in the linear growth rate follows because of three-dimensional (3D,
spherical) growth resulting in the transformed volume increased in proportion to Ġ 3.
Equation (2.35) corresponds to sigmoidal transformations, when F(t)] first in-
creases exponentially in time slowing down thereafter and finally asymptotically
approaching complete transformation. A simplified version of the Johnson–Mehl
equation, known as the Avrami or Avrami–Erofeev equation, is very often used in
practice:
n
FðtÞ = 1 − e − kt (2:36)
where n is known as the Avrami exponent and k is a parameter comprising both the
nucleation and growth rates associated with the phase transformation.
From the discussion presented above it is possible to identify some key engi-
neering issues related to precipitation. As concentration is changing during the pro-
cess quality of the product can vary even for precipitation of a single component.
This can be overcome by precipitation in a buffer solution of an electrolyte with pH
corresponding to the pH of precipitation. An alternative method is continuous pre-
cipitation when pH and concentration is constant when the precursors are fed into
the reactor and the precipitated suspension is removed continuously. Application
of the proper solvent and pH also influences the crystal shape. Habitat (or crystal
shape) can be important for either technological reasons (improving rheological
properties, downstream operations, handling, etc.) or from the viewpoint of cata-
lytic behavior. The rate of cooling or evaporation, the degree of supersaturation,
crystallization temperature and presence of impurities can influence the crystal
shape. In particular, adsorption of impurities blocking the crystal surface may
change the crystal shape or decrease the growth rate. Therefore, impurities can be
removed prior to crystallization or alternatively can be added influencing the crys-
tal habit. Moreover, the precipitate can contain some impurities or ions that might
influence catalytic performance. A remedy is to apply decomposable ions, such as
nitrates, oxalates or ammonium.
Supersaturation degree can be different in different parts of the vessel. In order
to avoid local supersaturation at the points when the solutions are mixed and
achieve homogeneous precipitation, it is possible to add another component (for
example, urea), which keeps the solution homogeneous at least for some time.

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For multicomponent precipitates it is even more difficult to achieve homogeneity

of the precipitate. Because of different solubilities, solid-phase composition could be
different at the beginning and at the end of precipitation. For example, precipitation
of hydroxides from a mixture does not occur simultaneously, but depends on the pH.
Tab. 2.4 contains values of pH at which hydroxides start to precipitate for 0.01 M sol-
utions and corresponding values of equilibrium constants KL = ½Men + ½OH − n are

also given for the equilibrium MeðOHÞn $ Men + + ½OH − n . For precipitation to
occur the term [Men+][OH−]n should exceed KL. Thus, during neutralization of acidic
solutions, when mixing is sufficient, formation will be observed in the solid phase of
a hydroxide with a lower value of precipitation pH. Co-precipitation of hydroxides
with similar precipitation pH results in the generation of complex crystal structures,
inclusion of one hydroxide into another one or adsorption of one hydroxide onto an-
other one, which is formed first, etc.
Tab. 2.4: Dependence of precipitation on pH for

hydroxides for 0.01 M solutions.
Hydroxide pH KL
−
Mg(OH) . (÷.) × 
Mn(OH) . . × −
Ni(OH) . −÷−
Zn(OH) . −
Cu(OH) . . × −
Cr(OH) . . × −
Al(OH) . . × −
In(OH) . . × −
Fe(OH) . . × −
(From [50].)
For low soluble compounds the mechanism of crystal formation is different from
the classical method and follows orientation attachment when larger crystals are
formed by crystallographically oriented assembly of smaller nanocrystals.
Aging follows nucleation and growth stages and allows the system to approach
thermodynamic stability. During aging there could be changes in the particle size
caused by dissolution-crystallization and aggregation, changes in the crystal phase
(for example, titania from anatase to rutile), crystallization of amorphous phases
and changes in morphology.
Washing, drying and calcination are typical preparation steps that are per-
formed after aging. A flow scheme of industrial-scale catalyst preparation by precip-
itation is given in Fig. 2.94.

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Mixed metal Sodium

nitrates tank carbonate tank
Filter
Mixed oxides
Drier and
and carbonates
calciner
Mill
Precipitation
and aging Powder mixing
bin
Weighing
machines Catalyst pellets
Pelleting machine
Fig. 2.94: Preparation of catalysts by precipitation. (From [51].)
This scheme is rather general including the most important unit operations
needed to prepare bulk oxides type of catalysts by precipitation. It is worth consid-
ering a specific case of copper- zinc-aluminum oxides catalyst used for methanol
synthesis.
Synthesis of this catalyst includes several steps, namely the preparation of sol-
utions, mixing, filtration, washing, drying, grinding, pelletizing, calcinations and
final packaging. Precursors of high purity are needed to make a catalyst with mini-
mal amount of impurities, giving highly dispersed or amorphous precipitates and
subsequently catalysts with developed surface area. The scheme of the catalyst
preparation is presented in Fig. 2.95.
Water solutions of the corresponding salts of copper and aluminum together
with sodium carbonate are fed into the reactor in (pos. 5), where 20–40 nm crys-
tals of copper carbonate are formed mixed with aluminum hydroxide particles of
a size < 15 nm. After the addition of zinc nitrate, small crystals of zinc carbonate
are generated that are included in the copper carbonate crystals, preventing the
growth of the latter. After filtration (pos. 6) from the mother liqueur, drying and
calcination (pos. 7), the crystals are ground (pos. 8) resulting in small particles.
Graphite (pos. 9) is then added to these particles, which after additional grinding
(pos. 11) are tabletized (pos. 12). The amount of graphite in the final catalyst is
below 2 wt%. Reduction (pos. 15) results in the formation of copper crystallites in-
corporated in the matrix of Al2O3-ZnAl2O4 spinel. The presence of zinc diminishes
dehydrogenation ability of the catalyst.

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Cu(NO3)2 Na2(CO3)2 Al(NO3)3 Zn(NO3)2

H2O H2O H2O H2O
1 2 3 4 Gas
Air
5
7
6
14 8
10
15
9
11
16
13 12
Fig. 2.95: Flow scheme of Cu-Zn-Al oxide catalyst preparation: 1, 4 vessels for preparation of
water solutions; 5, reactor; 6, filter; 7, drying and calcination unit; 8, grinder; 9, vessel with
graphite; 10, mixing and conveyer; 11, additional grinding unit; 12, tabletizing machine; 13 and
14, conveyers; 15, reactor for reduction (or oxidation); 16, vessels for the final catalyst. (From
[52]).
2.3.4 Heteropoly acids
Heteropoly acids (HPA) or polyoxometalates are an interesting class of bulk acid

catalysts with the anion [XxMmOy](–q) balanced by protons. In heteropoly acids X
stands for a hetero atom, such as B, Al, Si, Ge and P, As or Fe, Mn, Co, Cu and
Zn. M indicates addenda atoms (Mo, W, V, Ta, Nb, Os), which are attached to hetero
atoms through oxygen atoms and q is the charge, varying from −3 to −28. Addenda
atoms typically have high charge (+5 or +6), small size with ionic radius in the
range 0.53Å–0.70Å, an expandable coordination number from 4 to 6 and the ability
to form double bonds with unshared oxygen atoms.
Well-known Keggin structures HnXM12O40 (H4Xn+M12O40, with X = Si, Ge; M = Mo,
W and H3X n+M12O40, with X = P, As; M = Mo, W, for example, H3PMo12O40 and H3
PW12O40) can possess such qualities as good thermal stability, high acidity and high
oxidizing ability and could be used as heterogeneous acid catalysis.

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Synthesis of H3PW12O40 can be done by dissolving Na2WO4 and Na2HPO4 in boil-

ing water and adding hydrochloric acid, leading to the precipitation of H3PW12O40·
nH2O, which is extracted with ether.
The thermal stability of HPA is, however, not sufficient for high temperature
applications, moreover the surface area of bulk heteropoly acids is rather low
(2–10 m2 g−1) and therefore activity is insufficient. Supported heteropoly acids can
be used to overcome these limitations. The key issues in the use of such supported
HPA are the retention of polyanion structure, proper dispersion and fixation to the
support. Typically, the choice of the support (γ-Al2O3, MgO, ZrO2, TiO2, activated
carbon, zeolites, mesoporous materials, clays or mixed oxides) is determined by a
need to have a high surface area, inertness and thermal stability.
2.3.5 Catalyst supports
Supported catalysts are often applied because they combine a relatively high dis-
persion (amount of active surface) with a high degree of thermostability of the cata-
lytic component. The important properties of the support are stability at reaction
and regeneration conditions, proper texture, thermal conductivity, mechanical
strength and low costs. Typically, different phases of alumina, silica, titania, zirco-
nia, magnesia, zinc oxide and active carbon are used.
The support should also enable production of shaped particles (mm range)
where small easily sintered crystals of the active phase (nm range) do not coalesce.
Pre-shaping of supports is an attractive option. However, care must be taken that
dispersion of the catalytic components is not modified in the following steps. With
powdered supports, the intimate mixing during deposition of the catalytic compo-
nents is easily realized during the first step, however, the following operations, in
which the grains are transformed into their required shape with desired porosity,
are more difficult and the dispersion may not be uniform.
2.3.5.1 Carbon
Active or activated carbon, together with alumina and silica, is mainly used as a cata-
lyst support. Activated carbon is preferred in applications where properties like inert-
ness, lower coke propensity compared to silica and alumina, stability at a wide range
of pH and temperatures, high adsorption capacity, wide variety of textural properties,
are of importance. Carbon supported noble metal catalysts are typically applied in
various liquid-phase hydrogenation reactions at rather low temperatures.
In oil refining the application of activated carbons is usually limited by chemical
reactivity in the presence of oxygen. This means that conventional methods of catalyst
regeneration by burning off the coke away are not applicable. Moreover, active car-
bons are mechanically weak, which prevents their applications in fixed-bed reactors

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and leads to generation of fines in slurry systems. Conversely, in order to recover the
active phase (expensive precious metals for example) from spent catalysts, carbon
can be easily burned away. It also should be noted that although conventional car-
bons are used mainly as powders, different forms, such as extrudates, cloths and
fibers could be prepared. Finally, the costs of carbon supports are usually lower than
other conventional support materials.
Activated carbon is produced from carbonaceous (for example, carbon rich)
source materials such as nutshells, wood and coal by physical or chemical activa-
tion. In the former case carbonization is used.
Once during a scientific presentation a PhD candidate, who happened to be the author of this
book, got a question related to selection of the support, which was active carbon. The person
who posed the questions was wondering why this particular support was used as it was active in
the reaction in addition to the metal on it. That person was assuming that the term “active” was
related to catalytic activity of the support and not the activation procedure during preparation.
Materials with carbon content are pyrolyzed at temperatures in the range 600–900 °C,
in the absence of air (usually in inert atmospheres with gases like argon or nitrogen)
(Fig. 2.96). This process is followed by activation/oxidation as carbonized material is
exposed to oxidizing atmospheres (carbon dioxide and/or steam at 400–600 °C).
Some carbon is burned away to give the porous structure. Chemical activation means
impregnation with, for instance, phosphoric acid or zinc chloride, and carbonization
at temperatures in the range of 400–600 °C. Carbonization/activation steps proceed
simultaneously. Activating chemicals remain in the structure after carbonization.
After washing, the final activated charcoal is produced. Activated carbons have a
much higher specific surface area than other types of supports (> 1,000 m2 g−1).
Peat, coal, biomass,

Carbonaceous material
sugar, polymers
High T
pyrolysis
Porous material
H2O
Partial gasification
Additional porosity Activated carbon
Fig. 2.96: Preparation of activated carbon.
All activated carbons have a porous structure, usually with a relatively small
amount of chemically bonded heteroatoms (mainly oxygen and hydrogen). In addi-
tion, activated carbon may contain up to 15% of mineral matter (the nature and
amount is a function of the precursor), which is usually given as ash content.

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The adsorptive properties of activated carbon are determined not only by its
porous structure but also by its chemical composition. In graphite, with a highly
oriented structure, the adsorption takes place mainly by the dispersion compo-
nent of the van der Waals forces, but the random ordering of the imperfect aro-
matic sheets in activated carbon result in incompletely saturated valences and
unpaired electrons, and this will influence the adsorption behavior, especially
for polar or polarizable molecules. In addition activated carbon is associated
with such heteroatoms as oxygen and nitrogen (derived either from the starting
material, activation process or post-treatment) and with the inorganic ash com-
ponents. The presence of oxygen and hydrogen in surface groups can be up to
30 mol% H and 15 mol% O, which has a large effect on the adsorptive properties
of the activated carbon. Some functional groups in carbon supports are given in
Fig. 2.97.
Quinone
O Free
Ethers
Phenolic O
radicals
HO
O
C
H OH
C O OH
O Phthalic
O
Aldehyde C
H
O
C
p-sites: O
Lactone
C6 rings, edge OH
>C=C< bonds HKCN
O
C7 and C5
Carbon C OH rings
Pyran O
chains O C O
H
Pyrone R
Carboxylic
Chromene
Fig. 2.97: Functional groups in activated carbon.
Oxidation with hydrogen peroxide and nitric acid results in the formation of C–O
bonds, lactones, quinine, and carboxyl-carbonate structures with higher acidity
generated by treatment with HNO3. Therefore, even if carbon is hydrophobic the
chemical nature could be modified to increase hydrophilicity.
In some cases, the high surface area of the carbon support may be detrimental
if the active catalytic phase is confined in narrow micropores that are not accessible
to the reactant molecules. This is important in processes where large molecules are
involved, for example, in liquid-phase reactions of fatty acids when diffusion of re-
actants and products may be hindered by the narrow porosity.

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Because activated carbons are lacking purity and could be hardly tunable mate-
rials with difficult to reproduce properties (even having the same surface area) sev-
eral attempts were made in academia and industry to synthesize a carbon support
that will be reproducible and mechanically stable. Thus, there is a growing interest
in making catalyst supports from carbon nanotubes and carbon nanofibers, which
could be produced in reproducible ways and make it possible to tailor the proper-
ties of these materials.
Carbon nanotubes (CNTs) that are categorized as single-walled (SWNTs) and
multi-walled nanotubes (MWNTs) possess a cylindrical nanostructure with a
length-to-diameter ratio of millions to one. They can be viewed as rolled, long, hol-
low structures with the walls formed by one-atom-thick sheets of carbon. High ther-
mal conductivity and special mechanical and electrical properties made them a
subject of intense research. The chemical bonding of nanotubes is composed of sp2
bonds, as they are stronger than sp3 bonds and thus result in materials with sub-
stantial mechanical strength. Single-walled nanotubes (SWNT) have a diameter of
close to 1 nm. Multi-walled nanotubes (MWNT) consist of multiple rolled layers of
graphene (Fig. 2.98).
(A) (B)
Fig. 2.98: Structure of (A) single wall- and (B) multiwall nanotubes.
Carbon nanotubes are prepared by catalytic vapor phase deposition of carbon that
uses an initial layer of metal catalyst particles, most commonly nickel, iron or co-
balt. The diameter of the nanotubes, which is controlled by annealing or plasma
etching of a metal layer, is related to the size of the metal particles. Nanotubes grow
at the metal catalyst sites where the carbon-containing gas (acetylene, ethylene or
methane) is dissociated on the surface and formed carbon is transported to the
edges of the catalyst particle, where the nanotubes are formed with the metal par-
ticles staying either as the nanotube base (Fig. 2.99, top) or rest at the tip of the
growing nanotube (Fig. 2.99, bottom) depending on the adhesion.

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Extrusion or root growth
CnHm
Metal
C C
Support
Tip growth
CnHm C +H2
Metal
Support
Fig. 2.99: Mechanisms of nanotubes growth. (Reproduced from [53]).
When CNT are used as catalyst supports they provide a spatial restriction on
the metal particles by adjusting the CNT diameter and sintering.
Removal of the initial catalytic material could be an issue in this method. If this
is done by an acid treatment (to remove alumina) the original structure of the car-
bon nanotubes could be destroyed.
Process-wise CNT can be synthesized in a flow reactor (Fig. 2.100) at ~700 °C to
which a carbon-containing gas is fed along with a process gas (for example, nitro-
gen or hydrogen).
When plasma is generated by applying a strong electric field using plasma en-
hanced chemical vapor deposition, the nanotubes grow in the direction of the elec-
tric field.
Fluidized bed reactors are used industrially for CNT preparation. The fluidized
bed pilot plant of 10 t year–1 developed by Arkema (Fig. 2.101A) for the production
of Graphistrength™ MWNT allowed for the synthesis of materials as highly en-
tangled bundles (Fig. 2.101B) with a size of several hundreds μm.
Similarly a fluidized bed reactor was used for the production of Baytubes®
(Fig. 2.102) resulting in agglomerates of multiwall nanotubes, where each tube (diame-
ter ~15 nm) comprises several graphite layers. The process, with an announced annual
capacity of 3,000 t, is claimed to provide high carbon yields and high space-time.

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Quartz
tube
Gas inlet Gas outlet
Quartz Sample
boat
C2H2N2
Oven 720 °C
Fig. 2.100: Scheme of CNT synthesis in a flow reactor.
100 µm
(A) (B)
Fig. 2.101: Production of CNT at Arkema. (A) Pilot plant photo, (B) SEM image of MWNT bundles.
(From [54]).
Filter/incineration unit
Catalyst
Heating
Fig. 2.102: CNT production in a fluidized bed (redrawn from

Hydrocarbons/H2/inert gas [55]).

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Carbon nanofibers (CNFs) are another material made of graphene layers, which
are high surface area materials (~200 m2 g−1). They are synthesized in a similar way
to CNT using the catalytic growth methodology with iron, cobalt and nickel as the
catalytically active metals. Graphical layers of different orientation can be formed,
for example, the fishbone type (Fig. 2.103).
Fig. 2.103: Electron microscopy of fishbone nanofibers. (Reproduced with permission from [56]).
Copyright (2012) American Chemical Society.
The thickness of the fibers can be controlled by the metal particle size, while the
graphite plane orientation depends on the growth temperature and the metal type
(parallel or fishbone types are formed with iron or nickel, respectively). The growth
rate influences the strength of the fibers, for example, slow growth of thick fibers
leads to strong particles.
2.3.5.2 Deposition of metals on carbon and surface charge of supports

Carbon is essentially hydrophobic in nature. It has low affinity for polar solvents
such as water and high affinity for non-polar solvents (acetone). When a metal, for
example, platinum, is deposited from water solutions of hexachloroplatinic acid, it
will be, therefore, located primarily at the outer surface. Application of acetone as a
solvent allows more uniform distribution along the catalyst grain.
Another important factor is the presence of oxygen surface groups. Because of
these surface groups carbon supports (as well as other supports, such as silica or alu-
mina, which will be discussed in the subsequent sections below) develop a pH-
dependent surface charge (Fig. 2.104A) when placed in an aqueous solution.
Dissociation of the acidic groups on the surface of a particle will lead to a negatively

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– +
– – + +
– ++ + – –
+ + – –
– +
+ + – + –– – +
+ – – +
– + + + – –
– +
– +
+ H+A– + B+OH–
(A) Acid pH Basic pH
40
20
0
ζ (mv)
–20
–40 IEP
–60
–80
–100
0 2 4 6 8 10 12
(B) pH
Fig. 2.104: (A) Surface polarization as a function of the solution pH. (B) Dependence of zeta
potential on solution pH for Norit carbon.
charged surface. A decrease of pH in the case of a negatively charged surface will

reduce the surface charge to zero (isoelectric point or point of zero charge). The basic
groups will attract a positive charge from the solution and an increase of pH will
counterbalance it. As the surface of the support is charged depending on the pH it
can accept either cations or anions. Thus, a special care should be taken during cata-
lyst preparation regarding the charge of the surface and the charge of species to be
deposited.
Figure 2.104(B) illustrates how the zeta potential of activated carbon Norit de-
pends on the solution pH.
Because of the surface charge there are more ions of the opposite charge in the
interfacial region around the particle. The electric double layer consists of two
zones: an inner region or Stern layer where the ions are strongly bound and the
outer layer (diffuse) with less firmly bound ions. A boundary in the diffuse layer
separates ions (which move when a particle moves, for example, because of grav-
ity), from those ions that stay in the bulk. Zeta potential reflects the potential at this
boundary. High values of zeta potential typically mean that the particles will repel
each other. As clearly seen from Fig. 2.104B zeta potential displays strong depen-
dence on pH in aqueous solutions. Figure 2.104B also illustrates that the position of

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the isoelectric point (IEP) is close to pH = 4.5. Below this pH the surface is positively
charged and will accept anions.
The thickness of the double layer depends on the concentration of ions in so-
lution. Some inorganic ions (for instance contaminants in the solution) strongly
adsorb on the surface and can thus strongly influence the zeta potential even if
they are present in low concentrations.
Although the oxygen group’s presence is beneficial for better metal dispersion,
it worsens reducibility of metals in a carbon supported catalyst, where carbon-
active phase interactions are typically weak.
2.3.5.3 Transition metal oxides

Transition metal oxides (e.g., titania, chromia, zirconia and vanadia) exhibiting var-
iable oxidation states, many crystallographic forms and thermal stability are widely
used as catalysts and supports in different catalytic reactions, including selective
oxidation, hydrogenation, selective dehydrogenation, alkylation, aldol condensa-
tion, carbonylation, amination and ammoxidation reactions to name a few. Surface
acidity and basicity as well as cationic/anionic vacancies make transition metal
oxides attractive for utilization in catalysis. A particular interesting application is
related to photocatalysts when titania, which is a wide band gap semiconductor, is
often implied for various reactions including solar water splitting.
Titanium dioxide TiO2, or titania, as a naturally occurring oxide of titanium, is
used in the form of nanoparticles, as a pigment in paints and in sun protection
creams. It is typically prepared by aqueous hydrolysis of titanium salts or flame
hydrolysis of TiCl4. Two crystalline forms of titania – anatase or rutile – compris-
ing chains of TiO6 octahedra are obtained depending on the preparation condi-
tions. Both rutile and anatase have tetragonal crystalline structure containing,
respectively, 6 and 12 atoms per unit cell. Anatase is formed as a metastable
phase with high surface area and can be then slowly transformed into a thermody-
namically more stable rutile.
Flame hydrolysis of titanium chloride leads to anatase with a surface area
40–80 m2 g–1 and mean pore diameter close to 50 nm. This phase is more stable at
high T and thus more suitable for catalytic applications. Aqueous hydrolysis of tita-
nium salts gives a support with the surface area of 190–200 m2 g–1 and a pore diam-
eter of 15–20 nm. Contrary to silica and alumina, which are insulators, titania is a
semiconductor and thus can be used as a photocatalyst. Moreover because of the
possibility of ready reduction of Ti+4 to Ti3+ the partially reduced titanium oxide
species can decorate supported metal nanoparticles, significantly changing the cat-
alytic properties because of strong metal support interactions.
There is a long history of using an aerosol flame method for the production of
titania (spherical particles of predominantly anatase) for various photocatalytic
reactions (such as titania marketed by Degussa as P25). It is not only titania that

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can be produced by this method but also other supports (alumina or silica) with
non-porous structure and high external surface areas, which includes exposure to
high temperatures and cooling rates. The resulting materials have good thermal
stability.
Aerosol flame synthesis can be classified into vapor-fed and liquid-fed
variants. In the vapor-fed methods applied for the synthesis of fumed silica and tita-
nia, volatile precursors (such as chlorides) are evaporated and fed into the flame.
For synthesis of titania, the flame is needed to ignite the process, while a hydrogen/
oxygen flame can also assist the process as in fumed silica manufacturing. The
metal precursor is first converted into the metal oxide, which undergoes nucleation
from the gas-phase. The schematic diagram is presented in Fig. 2.105A. A drawback
of the method is associated with limited availability of a volatile precursor at a com-
petitive price. In flame or flame-assisted spray pyrolysis liquid precursors are intro-
duced as either non-combustible (FASP, Fig. 2.105B) or combustible (FSP,
Fig. 2.105C). The main advantage of this method is the formation of nanosized par-
ticles with possible size control through the precursor-solvent composition.
A B C
Vapor-fed Flame- Flame

aerosol assisted spray
flame spray pyrolysis
synthesis pyrolysis
Nozzle
HC or H2/O2 HC or H2/O2
or air or air Dispersion gas
Aqueous O2 or air
Precursor Evaporator precursor Atomizer
solution Organic
precursor
solution
Fig. 2.105: Various flame configurations. (Redrawn from [57]).
The schematic picture of the particles formation is illustrated in Fig. 2.106.

For other common catalyst supports, such as silica or alumina, the flame meth-
ods result in highly aggregated structures. In general, the final particle size of the
solid material depends on the droplet size, gas velocity of the spray or the residence
time in the reactor and quenching efficiency. The flame process is influenced by a
number of parameters, such as gas and liquid-feed rates, type and concentration of
the precursor and solvent, solvent-to-fuel ratio. For instance, nucleation and coagu-
lation rates are increased at high liquid-feed rates, which results in enhanced

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Hollow Large Small

particles particles particles
Nucleation
Intraparticle Intraparticle Precursor Product
conversion conversion vapor vapor
and collapse
conversion
Precursor
evaporation
Solvent and
precursor
Solvent evaporation and
precursor precipitation
Precursor
Droplet Droplet vapor
(Flame-assisted) Flame spray Vapour-fed aerosol

spray pyrolysis pyrolysis flame synthesis
Fig. 2.106: Schematics of the particle formation. (Redrawn from [57]).
particle growth. Conversely, a reduction of the overall particle growth is achieved at

lower flame temperatures and thus allows for faster cooling. This in turn is possible
at high dispersion gas-flow rates. However, because of the complexity of flame
methods, precise control over the size is not easy and the particles exhibit generally
a wide particle size distribution.
Moreover, complete crystallization is difficult to achieve in conditions of very
short residence times at high temperatures and fast cooling rates. This can result in
partially amorphous materials restricting the use of flame methods for synthesis of
catalyst supports when high crystallinity is needed.
As flame pyrolysis methods give materials with high thermal stability, in addi-
tion to titania such supports such as ceria are also produced by these methods.
Such thermo-stability is important for automotive exhaust applications.
Ceria along with zirconia are bifunctional catalysts and contain both acid and
base sites, which obviously make them attractive in bifunctional heterogeneous
catalytic reactions as well as in catalytic conversion of CO2 to value-added chem-
icals. In particular, appealing are the high oxygen mobility and redox property of
CeO2.
Zirconia is formed mainly in tetragonal and monoclinic crystallographic
phases. The former phase is metastable, possessing a high surface area, while the
monoclinic form is thermodynamically stable.

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2.3.5.4 Silica
The amorphous silica supports are typically used in applications that require rela-
tively low temperatures, as it has lower thermal stability when compared to alumina.
Moreover, under exposure to steam volatile hydroxides can be formed at elevated
temperatures. By its chemical nature, silica is a weak acid and is more resistant than
alumina to acidic media.
Two different methods are used for preparation of silica supports: flame hydro-
lysis giving fumed silica and sol-gel precipitation leading to silica gels.
Flamed or fumed silica is a very pure material with nanometer sized dense par-
ticles (40–50 nm) not possessing micropores. The surface area is up to 300 m2 g−1
and the diameter of pores is above 7 nm. This type of silica is manufactured by
flame hydrolysis of SiCl4, which is first formed by carbo chlorination of a macro-
scopic oxide:
SiO2 + C + 2Cl2 ! SiCl4 + CO2
Silicon tetrachloride then reacts in a flame reactor where (in addition to

SiCl4) hydrogen and oxygen (air) are fed, leading to the following reactions:
2H2 O + O2 ! 2H2 O, SiCl4 + 2H2 O ! SiO2 + 4HCl. Nanometer sized silica particles are
separated from HCl in a cyclone followed by deacidification of the silica surface with
steam and air in a fluidized bed downstream of the cyclone (Fig. 2.107). Formed silica
has a low density and needs to be compacted prior to forming operations in a com-
pactor, located downstream of a fluidized bed reactor and a hopper. Process parame-
ters such as flame temperature, content of the substrate, hydrogen to oxygen ratio
and the residence time allows control of the size and aggregation of silica.
Hydrogen To HCl absorption
Oxygen (air) Cyclone
Mixer
Burner
Vaporizer
Silicon tetrachloride Pyrogenic

Deacidi- silica
Cooler
fication
Fig. 2.107: A flow scheme of fumed silica production. (From [51].)
In the sol-gel route the alkaline solution of sodium or potassium silicate (for exam-
ple, the pH of water glass for sodium silicate is 12) is mixed with sulfuric acid,

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which triggers the formation of first Si(OH)4 monomer units, followed by polymeri-
zation to a colloidal solution (sol) where silanol (Si–OH) groups and Si–O–Si bonds
are formed. Minimization of –OH and maximization of Si–O–Si bonds is the driving
thermodynamic force for the formation of oligomers and cyclic species, small par-
ticles and eventually larger particles. Colloidal solutions are formed by micelles,
which are separated because of repelling electric charges on their surface and in
the solution, prohibiting coagulation. Sodium ions play a critical role in controlling
agglomeration of micelles. At some point the sol undergoes gelation – the formation
of a 3D hydrogel (Fig. 2.108). Gelation depends on the micelle concentration, tem-
perature, ionic strength and especially pH.
OH HO OH HO OH HO
OH
OH Si HO
HO Si Si OH
HO Si OH Si
O O O O O O Si
Sol O
O O
OH O
Gel
Fig. 2.108: Formation of a gel.
The key factors are the rates of hydrolysis –M–O–Na(R) + H2O → –MOH + Na(R) OH
condensation –MOH + XOM → M–OM + XOH, where X = H, R. R indicates that pre-
cursors in sol-gel synthesis could be not only salts such as metal silicates, but also
alkoxides. If hydrolysis is faster than condensation then the material is less
branched, while slower hydrolysis leads to a highly branched one.
The gelation rate is slow at low and high pH and can range from minutes to
days. The density of hydrogel, which is a metastable polymer, increases with an in-
crease of the initial salt concentration and gelation rate. The subsequent steps in
the preparation of silica are washing of the gel to remove sodium and then drying.
The drying is critical in producing a material that could be used as a catalyst sup-
port. Dried material can occupy 5% of the original hydrated gel volume. Drying at
moderate temperatures (150–200 °C) leads to the collapse of pores, drastic reduc-
tion of porosity and formation of xerogels, which lack macropores and the sufficient
strength for them to be used in fixed-bed reactors. These xerogels are first milled to
the desired size and mixed with binders prior to shaping. An alternative to this pro-
cedure is drying under supercritical conditions leading to aerogels. First a less
polar then water solvent (i.e., acetone) is used to wash away water and then ace-
tone itself is washed away with high-pressure liquid carbon dioxide. After heating

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Silicate Acid
Mixing
Washing
Drying
Classification Milling
Packaging
Fig. 2.109: Preparation of silica by sol-gel method. (From [51].)
beyond the critical point and gradually releasing pressure a dried product is
formed. The flow scheme of silica preparation is illustrated in Fig. 2.109.
After drying at a low temperature the concentration of silanol groups is high
(4–5 OH per nm2) and the material is hydrophilic. Heating at a high temperature
results in dehydroxylation, and thus a decrease in concentration leading to hydro-
phobic surfaces. The surface area of commercially available silica supports varies
between 400–700 m2 g−1 with an average pore diameter of 2.5–5 nm depending on
the preparation conditions.
The surface charge of silica depends on pH (Fig. 2.110). At pH equal to the point
zero charge (pH ~2) the surface is neutral with –SiOH groups, while at acidic and
basic pH the main surface groups are –Si–OH2+ and –SiO–, respectively.
In addition to colloidal and fumed silica, another type of silica – kieselguhr –
found an application as a support for vanadium pentoxide catalysts, which are ap-
plied in oxidation of SO2 to SO3. Diatomaceous earth (diatomite) kieselguhr is a
form of silica composed of the siliceous shells of unicellular aquatic plants of micro-
scopic size. This material is heat resistant and has been used as an insulator, as a
component in toothpaste and as an abrasive in metal polishes. Kieselguhr, with a
surface area of 20–40 m2 g−1 and a broad range of pore sizes, contains small
amounts of alumina and iron as part of the skeletal structure.

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10
0
–10
–20
ζ (mv)
IEP
–30
–40
–50
–60
–70
0 2 4 6 8 10 12
pH
Fig. 2.110: Zeta potential as function of pH for silica.
2.3.5.5 Alumina
Although a variety of alumina exists, distinguishable by XRD, only a few phases
are applied as catalyst supports, such as non-porous low surface area crystalline
α-alumina, and porous amorphous η and γ-alumina. Annual world production of
alumina is approximately 45 million tons, over 90% of which is used in the manu-
facture of aluminum metal.
Aluminum is extracted from bauxite, an ore containing aluminum hydroxide, sil-
ica and other oxides by treating it with sodium hydroxide. Formed sodium aluminate
Na2O·Al2O3 (or Na2Al2O4) undergoes crystallization that leads to different gels de-
pending on the pH. This is done by adding nitric acid to sodium aluminate. When
precipitation occurs at 8 < pH < 11 bayerite (Al(OH)3) is formed, which upon aging at
high pH gives gibbsite gel with the same chemical formula of aluminum hydroxide.
Precipitation at a lower pH (6 < pH < 8) results in crystalline boehmite gel AlOOH.
Different calcination procedures result in various phases of alumina (Fig. 2.111).
In cases when the presence of alkali might influence catalytic performance,
an alternative to the above mentioned route should be used. Alkali-free alu-
mina could be prepared from aluminum sulfates (Fig. 2.111) or aluminum alco-
holates. Both alkali and alkali-free methods result in high amounts of acids
and bases needed (2–4 t per ton of alumina), which are cumbersome to regen-
erate. γ-Alumina has a surface area in the range 50–300 m2 g−1 and pores between
5–15 nm. Rather high thermal and mechanical stability also makes alumina a popu-
lar support for various applications. The surface of alumina contains Brønsted acid
sites (H+ donors), Brønsted basic sites (acceptors of protons) and Lewis acid sites
(electron acceptors). After dehydroxylation the surface of alumina contains mainly
Lewis acidity,
O– OH O–
+ H+
O Al O Al O Al O Al
Lewis site Basic site Brønsted acid sites

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Al-sulfate solution Na-aluminate solution

Al2O3.3SO3 Na2O.Al2O3
pH < 2 pH > 12
+ +
Base Acid
At 3 < pH < 6 At 6 < pH < 8 At 8 < pH < 11

precipitation of micro precipitation of precipitation of
crystalline boehmite gel crystalline boehmite gel bayerite gel Gibbsite gel
AlO(OH) AlO(OH) Al(OH)3 Al(OH)3
Heating above 770 K Aging at pH 8 and 353 K Aging at high pH
Amorphous Al2O3 γ-Al2O3 η-Al2O3 𝜒-Al2O3

Spinel structure: cubic close packing
Heating at about 1,170–1,270 K
θ-Al2O3 δ-Al2O3 α-Al2O3

Heating above 1,370 K
α-Al2O3
Corund structure: hexagonal close packing
Fig. 2.111: Preparation of different alumina phases. (From [51].)
– – –
100 +++++ + +
+
Al2O3
80
Zeta potential (mV)
60
40
20
0
0
2 4 6 8 10 12 14
–20
+ + +
–40 Isoelectric point
–––––––
(zero surface charge
–60 at pH = 7.5–9) Al2O3
Fig. 2.112: Zeta potential dependence on pH.
In water solutions, the surface charge depends on pH, with the isoelectric point
close to 7 (Fig. 2.112).
Heat treatment of γ-alumina at temperatures above 1,370 K results in the forma-
tion of first θ alumina and then α-alumina (corundum). Simultaneously, the pri-
mary particles of γ-alumina grow in size to 70 nm for α-alumina concomitant with

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the reduction of the surface area (few m2 g−1). The latter phase of alumina found its
niche in high temperature applications, such as steam reforming of natural gas,
which will be discussed in detail in Chapter 4. The use of additives such as oxides
of chromium, iron, molybdenum or HF allows for lowering the temperature of
phase transformations and even avoiding the formation of the θ alumina phase. In
practice ammonium fluoride is used instead of hydrofluoric acid, as it decomposes
to NH3 and HF. HF adsorbs on the surface of γ -alumina at ~700 °C followed by
polymorphic transformations of γ -alumina to α-alumina at 700–1,000 °C. Although
the surface area of the product is ~10 m2 g−1, the total porosity (~0.55 cm3 g−1) could
be preserved in this preparation procedure.
2.3.5.6 Zeolites
A special type of supports, which are widely used as catalysts, are solid acids called
zeolites. Zeolites are hydrated aluminosilicate minerals with a microporous struc-
ture. The term was originally coined in the 18th century by a Swedish mineralogist
A. F. Cronstedt who observed, upon rapidly heating a natural mineral that the
stones began to dance about as the water evaporated. Using the Greek words which
mean “stone that boils”, he called this material zeolite. Zeolites are crystalline alu-
minosilicates containing pores and cavities of molecular dimensions. There are
close to 50 natural zeolites and almost triple this amount of synthetic zeolites that
do not occur in nature. The synthetic zeolites are among the most widely used sorb-
ents, catalysts and ion exchange materials in the world. Zeolite crystals are porous
on a molecular scale, their structures revealing regular arrays of channels and cavi-
ties (~3–15 Å), creating a nanoscale labyrinth. The complicated structure of zeolites
is constructed from several secondary building blocks with different number of
units, possessing 6, 8, 10 or 12-membered rings of T-atoms (Si, Al). Properties of
some zeolites are presented in Tab. 2.5 and Fig. 2.113.
Channels contain water molecules and alkali metal cations (M I, MII), which
can be ion-exchanged. The general formula of zeolites is MI MII0.5[(AlO2)x*(SiO2)y*
(H2O)z]. In addition to Al, silicon in the T atom position could be replaced, for exam-
ple, by P, Ti, Ga, Ge, Hf or Zr. Ions should have a coordination number of four with
the respect to oxygen and an ionic radius that fits into the zeolitic framework. An
interesting example of molecular sieves is VPI-5, which is an aluminophosphate
with a pore aperture of 1.2 nm. Such materials are electrically neutral and thus
largely catalytically inactive.
The key properties of zeolites are size and shape selectivity, together with the
potential for strong acidity. In zeolites SiO4 and AlO4 tetrahedra linked through com-
mon oxygen atoms and cations (such as Na+) are needed to neutralize the charge dif-
ference between Al3+ and Si4+. Brønsted acidity appears when Si4+ is replaced by Al3+
and the charge is balanced by proton, localized in vicinity of Al. Zeolites could thus
have acidities compared to mineral acids. Acidity depends on the Si/Al ratio. With an

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Tab. 2.5: Properties of zeolites (From [29]).
Common Three-letter Channels Window or Pore Si/Al

name code channel volume
diameter (nm) (cm g−)
Zeolite A LTA D, Cages connected by windows, . . 

cubic
Zeolite X FAU D, Cages connected by windows, . . –.
tetragonal
Zeolite Y FAU D, Cages connected by windows, . . >.
tetragonal
Mordenite MOR D, two straight, parallel .; . . >
channels
Zeolite L LTL D, one straight channel
ZSM- MFI D, one straight, one sinusoidal, . . >
mutually perpendicular channels
Zeolite BEA D, two straight, one sinusoidal, .; . . >
Beta perpendicular channels
Fig. 2.113: Various types of zeolites with different numbers of T-atoms (copyright [58]).
increase of Si content, Lewis acidity decreases and is zero for silica. Brønsted acidity
(zero for alumina) starts to be seen at Si/Al ~0.3, has a maximum at Si/Al ~3, and is
zero for silica. An empirical Lowensteins’ rule determines the structure of linkages in
zeolites, stating that Al-O-Al linkages are forbidden and thus Si/Al ratio must be
above or equal to unity. In fact, Si/Al ratio varies from 1 (LTA) to infinity (pure SiO2).

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Zeolites with a low aluminum content are hydrophobic (and vice versa). Zeolites are
thermally stable and if deactivated could be regenerated by simply burning the car-
bon deposits. Stability of zeolites increases with Si/Al ratio.
Usually the as-synthesized forms of zeolites (typically with Na+ balancing the
charge) are not the most suitable for the catalytic purposes. Acidity can be intro-
duced in the as-synthesized zeolite by ion-exchanging sodium cations with NH4Cl
or NH4NO3 to achieve an ammonium form. The ammonium form of zeolite is dried
and calcined to obtain the proton form of zeolite. The exchange of extra-framework
species (for example, Na+ to NH4 and H+) is one of the ways that zeolites structure
modifications. Other methods include dealumination by steaming or acid treatment
in order to change Si/Al ratio. Removal of aluminum from the framework by, for
example, hydrothermal treatment with steam at 600–900 °C leads to an ultrastable
zeolite Y, industrially used as a catalyst for catalytic cracking.
Incorporation of transition metals into zeolites gives rise to bifunctional cataly-
sis, where both metal and acid centers are involved in a catalytic reaction.
Incorporation of Pt into zeolites tested in a ring opening of decalin (Fig. 2.114A), re-
sulted in a decrease of the amount of strong acid sites while the overall number of
acid sites was almost unchanged (Fig. 2.114B). As a consequence, the amount of
cracking products decreased with a simultaneous increase in selectivity towards de-
sired ring-opening products.
cis- and trans-decalin Cracking products

CH3 200
CH3
Concentration of BAS (μmol/g)
H3C 180
CH3 160
140
120
100
CH3 CH3
80
H3C H3C
CH3 60
CH3
40
CH3 CH3
CH3 20
H3C
0
Weak Medium Strong
Decalin isomers Ring-opening products Strength of Brønsted acid sites (BAS)
(A) (B)
Fig. 2.114: (A) Ring opening of decalin and (B) concentration of Brønsted acid sites after
incorporation of Pt into zeolites. (Data from [59]).
In general, non-uniform distribution of aluminum leads to materials with different

acid strength. Acidity of zeolites is probed by mainly non-aqueous spectroscopic
methods (IR spectroscopy of probe molecules) and temperature-programmed de-
sorption of bases, giving information on the total amount of acid sites and the acid
sites distribution.

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For water non-sensitive materials, for example, acidic amorphous oxides or

active carbons, acidity could be determined by titration of aqueous slurries of the
acidic solids with a standard base.
Although catalytic activity of zeolites is often related to Brønsted acidity (for ex-
ample, the presence of protons) they also contain Lewis sites (coordinatively unsat-
urated Al+3 ions).
Zeolites are microporous materials with pore diameters below 2 nm, which re-
sults in some interesting selectivity properties. Thus an important property of zeolites
is shape selectivity, which refers to reactants (Fig. 2.115A), product (Fig. 2.115A) or
transition state selectivity (Fig. 2.116). Fig. 2.115A illustrates that in the case of a zeo-
lite with narrow pores, reactants with bulky substituents cannot enter the pores. For
product selectivity (Fig. 2.115B) only p-xylene can diffuse out of the ZSM-5 channel
pores, while o-xylene and m-xylene cannot be formed. Some transition state inter-
mediates are too large to be accommodated within the pores/cavities of the zeolites,
even though diffusion of neither the reactants nor the products is restricted. This is
the case for transition state selectivity (Fig. 2.116). The diameter of the cage is impor-
tant for the reactant and transition state selectivity, while diameter and the pore
length are the critical parameters for the product selectivity. In some instances coking
to reduce the pore size can be a method to improve shape selectivity.
Ca/X
OH
+ H2O
OH
Active site
OH
+ H2O
OH
(A) Ca/A
CH3OH +
(B)
Fig. 2.115: (A) Reactant and (B) product selectivity in zeolites.
Aluminosilicate zeolites are formed by hydrothermal synthesis, typically under

mild conditions (350–525 K) and autogenous pressure (above 373 K). Zeolites are
synthesized by mixing a silica source (the primary building units of the framework,

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Fig. 2.116: Transition state selectivity.
i.e., SiO2), an alumina source (origin of the framework charge), organic templates,
mineralizing agents (OH– anion, NaOH) and water (as solvent) to form an alumino-
silicate gel. The process in illustrated in Fig. 2.117.
SiO2 source
Liquid-phase-
Colloidal SiO2 mediated Crystals
Waterglass (Na silicate) transformation
Pyrogenic SiO2
Si alkoxide (SiOEt)4
Nuclei
AIO2 source
AI + NaOH Hydrogel/
NaAIO2 (pseudoboehmite) Precursors
precipitate
gibbsite
AI alkoxides
SDA: structure-directing agent

Mineralizers (catalysts)
Cationic organics (tetraalkylamines)
Neutral organics (solvents, amines) Salts (alkali, alkaline earth)
OH-
F-
Fig. 2.117: Schematic representation of zeolitization. (Reproduced with permission from [60]).
After initial transformation of Si, Al sources and the structure directing agent (SDA)
through the liquid phase mediation into a hydrogel or precipitate, the latter is con-
verted into precursor species. Such species assemble into nuclei, which then grow in
crystal according to classical crystallization. SDAs act as topology-determining

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templates while transformations of the gel to precursor/nuclei are thought to be cata-

lyzed by mineralizing agents such as alkali (alkaline earth) salts and OH−. Figure 2.118
illustrates the crystal growth of zeolites exhibiting typical S-shaped crystallization
curves [61] with an induction period.
(a) Nucleation rate (b) Crystal growth rate
Gel diffusion Nucleation Crystal growth

to equilibrate process
composition
Time
(c)
Polymerization
and nucleation Crystal growth
Structure-directing
T (Si,Al,Ti,....) precursors Mineralizers (OH-,F-)
agents
Fig. 2.118: Schematic representation of the (a) nucleation rate and (b) crystal growth rate of
zeolites described with a typical S-shaped curve and (c) related rearrangements from amorphous
particles into crystalline zeolite during the synthesis (Reproduced with permission from [61]).
Templates of the NR4+ type are used, such as tetra-alkylammonium hydroxide.

Alkylphosphonium cations (R4P+) and organic complexes can be also applied.
Reactants are mixed according to a synthesis recipe. Usually, different solutions are
prepared under continuous stirring and mixed to obtain a unique thick milky white
gel. pH of the solutions is an important control parameter. Other critical parameters
are: the molar ratios (OH–/SiO2 and Si/Al); temperature; the sources of silica and
alumina; presence of contaminants; the order of the addition of the reactants;
aging and ripening prior to crystallization; synthesis time; the nature of the organic
templates; pre-treatment of the reactants; inclusion of special additives; presence
of seeds and stirring rate and so on.

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In laboratory-scale preparations, once the gel is ready it is transferred to

Teflon-lined autoclaves, where the nucleation and crystallization of the gel takes
place. Condensation reactions occur faster than hydrolysis which leads to formation
of nuclei and growth by the addition/condensation of monomers. The particles are
negatively charged, preventing the formation of aggregates.
The Teflon-lined autoclaves are put in an oven with a constant predetermined
temperature for a period of time according to the synthesis procedure. In a labora-
tory scale, crystallization can be performed in a static mode, under internal rotation
or under rotation of the autoclaves.
When the crystallinity is plotted as a function of time, S-shapes curved are usu-
ally obtained (Fig. 2.118, 2.119), where the fraction of the transformed material F can
be described by the Avrami-Erofeev equation (eq. 2.36). with n determined by data
fitting. S-shaped features are caused by autocatalytic behavior at low conversions
because of slow nucleation and decline of the crystal growth rate with an increase
in crystallinity.
2.5
Av. crystal size (µm)
1.5
0.5
20 µm
0
0 20 40 60 80 (B)
(A) Time (h)
5 µm
(C)
Fig. 2.119: Effect of synthesis time on ZSM-5 zeolite. (A) Average crystal size as a function of synthesis
time, (B) morphology after 6 h, (C) morphology after 72 h. (Reproduced with permission from [62]).
An increase of the synthesis temperature at constant alkalinity (pH) increases nu-

cleation and linear growth rate. The induction time in zeolite crystallization de-
creases rapidly with an increasing temperature, up to a certain point. Similarly, the

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induction time decreases and crystal growth is enhanced by an increase in pH at

constant temperature. Alkalinity also has an effect on the Si:Al ratio of the zeolite.
After crystallization, the autoclaves are quenched with cold water. The formed zeo-
lite crystals are filtered, washed and dried. Washing is required to reduce high alkalin-
ity created by the addition of NaOH. In order to remove the organic template, zeolites
are typically calcined after drying (100 °C). A calcination step is needed to remove
the SDA. It is performed at 500–600 °C for several hours, depending on the zeolite.
Different calcination techniques have an effect on the properties of the synthesized zeo-
lite. After calcination, the zeolite is in the sodium form (the as-synthesized form, de-
noted by Na at the beginning of the name, for example, Na-ZSM-5) because it contains
sodium ions to balance the framework charge induced by Al as T-atoms. Acidity can be
introduced in the as-synthesized zeolite by ion-exchanging sodium cations with NH4Cl
or NH4NO3 to achieve an ammonium form. The ammonium form of zeolite is dried and
calcined to obtain the proton form of zeolite.
A flow sheet for the preparation of a sodium form of zeolites is given in Fig. 2.120.
NaOH Al-source H2O Si-source
Vapor
Fresh-
water
Product to
drying and
Mixing vessels crushing
Belt conveyer
Slurry
Vapor
Slurry
Crystallization
Concentrated mother liquor
Fig. 2.120: Preparation of a sodium form of zeolites. (From [51]).
The catalyst in the final process always requires further fine-tuning by a number of
secondary treatments. It is worth considering as an example the production of fluid
catalytic cracking catalysts. Detailed description of these catalysts is given in
Chapter 4. Typical commercial cracking catalysts are a mixture of rare earth-Y zeo-
lite and SiO2–Al2O3 amorphous aluminosilicate as a binder providing the required
mechanical stability. Small pore ZSM-5 is applied as a co-catalyst with rare earths Y
zeolite to increase the octane number of gasoline. The sodium form of zeolites Y is

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first produced followed by an exchange of sodium with rare earth ions, which is an
example of a secondary treatment. Although there is a clear advantage to using
binders the drawbacks are associated with blocking of the zeolites pores by the
binder and longer diffusion paths. The flow scheme for the production of rare earth
zeolites Y is given in Fig. 2.121.
Al2(SO4)3
RE(NO3)2
NH4NO3
Na2SiO3
NaAlO2
H2O
H2O
H2O
H2O
H2O
NaOH Al2(SO4)3
1 2 3 4 5 Na2SiO3
6 7 8
NH4NO3
NaAlO2
H2O 9
H2O
H2O Zeolite
10 14 H2O
11 13 15 17
H 2O H2O
16 REY
18
Fig. 2.121: Synthesis of rare earth zeolite. (From [52].) 1, 2, 3, 4, 5 = vessels for ammonium nitrate,
rare earth nitrate, NaAlO2, Al2(SO4)3 18 H2O and sodium silicate respectively; 6, reactor for sodium
aluminosilicate synthesis; 7,crystallizer; 8, crystallizer for synthesis of zeolite seeds; 9, filter; 10,
vessel for ion exchange of NH4+ into rare earths; 11, milling; 12, heat exchanger; 13, vessel of
additional ion exchange of NH4+ into rare earths; 14 cooler; 15, mixer; 16, filter; 17, vessel for
repulping of zeolite; 18, suspension storage. RE, a rare earth element.
Water solutions of ammonium nitrate, rare earth nitrate, NaAlO2, sodium silicate and
aluminum sulfate are prepared in vessels 1–5. Sodium aluminosilicate gel is obtained
in vessel 6 and a solution of NaAlO2 is added. After cooling, the mixture is routed to a
crystallizer in 7 to which a seed of zeolites Y is added from vessel 8 in the quantities
corresponding to 1–3 wt%. Mixing of the Na-Y zeolites seed with the reacting mixture
in vessel 7 lasts for ~1 h, thereafter hydrothermal synthesis is performed for ~24 h at
371 K followed by cooling to room temperature. After filtration (pos. 9) the mother
liquor is separated and the zeolites are washed with water and ammonium nitrate to
ion exchange sodium for ammonium. This is followed by primary ion exchange with

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rare earth (Ln3+) nitrates in vessel 10. After milling (pos. 11) and additional ion
exchange (pos. 13) at an elevated temperature (up to 473 K) the zeolite is cooled
(pos. 14), filtered (pos. 16) and transported to a vessel 17. From this vessel it is taken
as rare earth zeolite Y or routed to another vessel for storing in the form of suspension
(pos. 18) to be used in the synthesis of, for example, microspherical FCC catalysts.
The flow scheme of the microspherical catalyst synthesis is given in Fig. 2.122.
NaOH Sand H2O

H2O REY
6
1 2 4
9
Al(OH)3 H2SO4 H2SO4
H2O
3 2 5 H2O
11
14 15
6
7 12
H2O
Air
(NH4)2SO4
17
8 13
H 2O
10
Steam
Gas 16
H2O Air
Fig. 2.122: Microspherical catalyst synthesis. (From [52].) 1, vessel for water glass synthesis;
2, filter; 3, vessel for the preparation of aluminum sulfate solution; 4, vessel for the preparation
of water glass solution; 5, vessel for preparation of aluminum sulfate solution with sulfuric acid;
6, coolers; 7, mixer for preparation of the sol of zeolitic aluminosilica gel; 8, column for
preparation of microspherical gel particles; 9, vessel for rare earth zeolite suspension; 10, vessel
for water solution of ammonium sulfate; 11, vessel for gel syneresis; 12, vessel for gel activation;
13, vessel for washing out microspherical gel particles from sulfate and other ions; 14, drying
column; 15, column for calcination; 16, burner for flue gases generation; 17, storage.
In vessel 1 (Fig. 2.122) sand, water and sodium hydroxide are introduced fol-
lowed by the preparation of water glass at 98–110 °C, which is filtered to remove

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unreacted sand particles (pos.2) and transported to vessel 4 where the solution of a
needed concentration is prepared. Aluminum sulfate is first prepared in vessel 3,
then filtered and transported to vessel 5, where a working solution of aluminum sul-
fate is prepared by adding sulfuric acid. This is necessary as otherwise the solution
containing the required amount of alumina is too basic, which will result in the
generation of a zeolite with overly large pores and lower bulk density. Vessel 9
contains water suspension of rare earth zeolite Y. Solutions from vessels 4, 5 and
9 are routed to a mixer-sprayer 7, where water glass, aluminum sulfate and the
rare earth zeolite Y suspension are mixed at the ratio to assure pH 7.5–8.6.
Microdroplets of 2–5 nm leave vessel 7 and enter the column 8, which is filled
(~3 m) with transformer oil. The microdroplets pass through the column at ~
10–12 °C to form the gel. The large column diameter (1.5 m) is needed to prevent
sticking of the gel to the vessel walls. A droplet passes through the transformer
oil in 8–11 s, while 5–8 s are needed for coagulation. The coagulation rate in-
creases with temperature increase and concentration of the parent solutions and
depends on pH and presence of electrolytes. As mentioned above, an acid is
added to the mixture to ensure the required coagulation rate. Passing through
oil, a gel of microspherical particles is formed that contains 90% water and 10%
dry substance. Syneresis (expulsion of a liquid from a gel) is done in vessel 11 at
40–50 °C for 6–24 h. Replacement of sodium ions by ammonium occurs in vessel
12 at 50–80 °C for another 6–12 h. In order to prevent removal of Al3+ and rare
earth ions during washing (pos. 13) they are added in small amounts to the
washing step while sodium, ammonium and sulfate ions are washed out.
Washed gel particles can be treated with water solutions of surfactants to pre-
vent the collapse of the gel structure during drying (pos. 14). Washing is fol-
lowed by drying of the zeolite (pos. 14) and calcination (pos. 15). The flue gases
needed for drying and calcination are generated by burning natural gas in the
presence of steam and air (pos. 16).
During drying the flue gases enter the dryer from the bottom, while zeolite
suspension falls in the opposite direction. Temperature along the dryer changes
from ~315–325 °C at the top to 475–485 °C at the bottom. This process leads to a
material with ~8–10% water. Calcination can be performed in a fluidized bed
(Fig. 2.123). The vertical vessel for calcination has an extended upper part, while
the bottom part has an inlet for flue gases. The amount of flue gases is con-
trolled to allow fluidization, while at the same time preventing carryover of
smaller particles. Calcination starts at 600–650 °C for 10 h, followed by a de-
crease in temperature of the flue gases leaving the burner. At 250–300 °C the
fuel is shut off, while air is still added. The gradual decrease of the catalyst tem-
perature for 4–6 h to 80–90 °C allows the transfer of the catalyst to metallic
drums for storage.

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Flue gases
2 Flue gases
Catalyst
Catalyst
Flue gases
Fig. 2.123: Fluidized bed calcination unit. (From [48].)
2.3.5.7 Metal organic frameworks

These materials with a very high surface area (1,800–3,000 m2 g−1) have inorganic
building blocks interconnected with organic linkers. The organic units are typically
mono-, di-, tri-, or tetravalent ligands. The structure and properties of the metal or-
ganic framework (MOF) are influenced by the choice of metal and the linker.
Similar to zeolites, MOFs exhibit shape selectivity with more flexibility of chemical
composition.
MOFs are synthesized by hydrothermal or solvothermal methods, although,
contrary to zeolites, organic ligands remain intact. A variety of options for post-
synthetic modification of MOFs is thus available. One example of the use of MOFs
in catalysis are 2D, square-grid MOFs containing single Pd(II) ions as nodes and
2-hydroxypyrimidinolates as struts (Fig. 2.124). If all the Pd centers are catalytically
active in reactions such as Suzuki C–C coupling, when redox oscillations of the
metal nodes between Pd(+2) and Pd(0) intermediates are needed to accomplish the
reactions, these changes in the coordination number would lead to destabilization
and potential destruction of the original framework.
For hydrogenation reactions on MOFs it is also possible that reactions occur on
the surface of MOF-encapsulated palladium nanoparticles.

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Fig. 2.124: A palladium 2-hydroxypyrimidinolate metal organic framework (MOF) used to catalyze
efficient oxidation of allylic alcohols to aldehydes. (From [63].) blue, N; red, O; yellow, Pd; gray, C;
light blue, Cl.
Besides high costs, the drawbacks of MOFs are air/moisture-sensitivity and

scaling up issues associated with their low-temperature stability, which limits the
application of MOFs in various catalytic reactions.
2.3.5.8 Mesoporous materials

Because of the limitations caused by zeolites having pores below 1.1–1.5 nm
there is an interest in materials with characteristics similar to zeolites in terms
of acidity but with larger pores. Such materials could separate and can catalyze
reactions with larger molecules, which are otherwise not able to penetrate into
the pores of zeolites. From the point of view of synthesis the size of the templat-
ing molecule determines whether ordered mesoporous materials or zeolites are
formed. Isolated short alkyl chain quaternary ions lead to formation of micropo-
rous materials, while self-assembled surfactant structures with long alkyl chain
quaternary ions (such as C16H33(CH3)3NH3+ Br–) the direct formation of mesopo-
rous molecular sieves (Fig. 2.125). In solution, surfactants can self-assemble to
form micelles, rods, sheets and 3D structures. Synthesis of mesoporous materials
is similar to zeolites, as it is also conducted in basic media.
One of the most famous examples of mesoporous materials is MCM-41 silicate,
which is highly ordered and even gives a diffraction pattern although the glass-like

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Self-assembly
Condensation
Surfactant
removal
Fig. 2.125: Formation of mesoporous materials. (Modified from [64].)
silicate walls are not crystalline. The pore size distribution in amorphous MCM-41 is
usually quite narrow although not as tightly defined as for zeolites.
Acidity of MCM-41 is much less than of zeolites, which along with rather expen-
sive templates somehow hinders potential use of this material as a catalyst despite
hundreds of published scientific papers.
Hexagonal mesoporous silica SBA-15 and cubic cage SBA-16 are two other in-
teresting materials that belong to the group of mesoporous materials. Hexagonal
mesoporous silica SBA-15 is synthesized in acidic media (pH 1–2) using a non-
ionic tri-block copolymer, such as pluronic P123 (PEO)20(PPO)70(PEO)20 or HO
(CH2CH2O)20–(CH2CH(CH3)O)70)–(CH2CH2O)20H containing poly(oxyethylene) PEO
and poly(oxypropylene) PPO units. Cylindrical micelles are formed with silica par-
ticles assembling around the template with hydrophobic heads and hydrophilic
tails.
SBA-15 has thicker pore walls than MCM-41 and possesses monodisperse pores
of 5–20 nm, while microporosity can be also introduced. Thermal and hydrothermal
stability is also higher than for MCM-41. Synthesis of mesoporous SBA-15 proceeds
through dissolving tri-block copolymer, preparation of gel in acidic media, ripening
of the gel at 373 K for 24 h, filtration, washing with distilled water, drying at 373 K
and calcination at 813 K.
2.3.5.9 Layered compounds

Layered compounds can be categorized into three classes: (a) neutral ones (e.g., bru-
cite, phosphates and chalcogenides), (b) compounds containing negatively charged
layers with compensating cations in the interlayer space (e.g., montmorillonite) and

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(c) materials containing positively charged layers with compensating anions in the
interlayer space, such as layered double hydroxides (e.g., hydrotalcites).
A specific feature of cations or anions in the interlayer space of this relatively
high surface area layered materials is related to their ability to ion exchange.
Another feature is related to swelling properties.
Cationic clays, which may exhibit both Brønsted and Lewis acid sites, contain
two types of sheets comprising Si(O,OH)4 tetrahedron and M(O,OH)6 octahedron
(M = Al3+, Mg2+, Fe3+ or Fe2+) as building units. They are typically synthesized from
minerals possessing negatively charged aluminosilicate layers compensated with
interlayer cations. The Brønsted acidity is due to OH groups, while Lewis acidity is
associated with Al3+ substituting Si4+ in tetrahedral sheets. Another parameter
influencing hydrophilic–hydrophobic properties is the type of an exchangeable
cation.
Pillaring of clays to develop large pore and strongly acidic materials was initiated
by replacing the interlayer exchangeable cations first in smectites with tetraalkylam-
monium ions. Organic pillared clay minerals are, however, thermally unstable at
high temperatures (above 250 °C), leading to the interlayer collapse. Below the de-
composition temperature, organic pillared clays can be, however, applied in catalysis
and adsorbents. Intercalation of clay minerals with inorganic species allows to gener-
ate pillared clays, which retain their micro- and mesoporosity after heating above
300 °C.
Natural and modified clays have found applications in various acid-catalyzed
reactions, including cracking and alkylation of aromatics, as well as in bulk and
fine chemical synthesis.
Hydrotalcites or anionic clays (Fig. 2.126) are layered double hydroxides of gen-
eral formula [M2+(1–x)M3+x(OH)2]x+(An-x/n) yH2O, where M2+ is typically Mg (or Ni, Zn,
Cu), and M3+ is typically Al, but can be Mn, Cr, Co or Fe, while A is any anion (e.g.,
CO23 − , NO3− , F– and Cl–). They are formed in nature by weathering of basalts or from
precipitation in saline water. A typical example of a hydrotalcite is Mg6 Al2CO3
(OH)16·4(H2O). The main application of hydrotalcites is in base-catalyzed organic
reactions.
Anions M2+ or M3+

Water molecules
OH-
Fig. 2.126: Structure of hydrotalcite.

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2.3.5.10 Ceramic and metallic monoliths and foams as catalyst supports

Ceramic and metallic monoliths are typically used as catalyst supports [65].
Ceramic monoliths are made from cordierite 2MgO × 2Al2O3 × 5SiO2 or mullite
3Al2O3 × SiO2 by extrusion with subsequent firing or by corrugation. This is followed
by washcoating with γ-, θ- and δ-alumina, enhancing the original surface area of
just few m2/g to approximately 100 m2/g. After washcoating again firing at an
appropriate temperature is performed. The components, having a similar thermal
coefficient of expansion, are able to withstand high operation temperature
(1,200–1,300 °C) as well as heating and cooling cycles without disintegrating.
Typical cordierite honeycombs contain 400–600 channels per square inch with
the wall thickness of approximately 0.15 mm.
Metallic monoliths, made of Fe-Cr-Al alloy by corrugation, have thinner walls
(ca. 0.05 mm), better warm-up properties and are more mechanically strong than
cordierite. Corrugation is followed by rolling up or folding into monoliths of re-
quired size and shape. A suitable oxide layer should be formed to allow adhesion of
the alumina washcoat.
As already mentioned previously the surface area of cordierite is low and the
active metal cannot be deposited directly on the monolith. Therefore, there is a
need for applying wash-coat to increase the surface area and to deposit the active
component, which is typically silica or alumina, on the wash-coat. A wash-coat
thickness varies in the range of 15–100 μm providing 15–30 m2 g−1 surface area. A
colloidal solution, for example, of bohemite alumina, can be used for wash-coating.
In addition to alumina, the slurry contains stabilizers and binders. Stabilizers
such as ceria, zirconia and barium oxide are added to the washcoat to prevent
phase changes at the higher temperatures or to improve catalytic performance. In
three-way automotive exhaust catalysts, cerium oxide acts as an oxygen sink ab-
sorbing it during lean operation and promotes the water-gas shift reaction generat-
ing hydrogen and thereby improving catalyst performance under rich conditions.
The same function of oxygen absorption under lean conditions is provided by bar-
ium oxide. Zirconia in the washcoat composition stabilizes and serves in the three-
way catalysts as a support for rhodium.
To ensure chemical and physical binding of the washcoat of the honeycomb
surface and filling the large macropores of the ceramics, alumina in slurry should
be ground, providing a size distribution mainly in the range of 1–10 mm that is com-
patible with the pores of the ceramic wall.
The pH is usually controlled when preparing the colloidal solution and the ac-
tive components can be incorporated both directly in the slurry or after the wash-
coating. Typically, the slurry contains 10–20 wt% of the solid material depending
on the monolith cell density. The laboratory procedure of wash-coating comprises
first dipping the monolith into the wash-coat slurry with forced flow. The wash-coat
slurry contains typically more than the calculated desired amount of the wash-coat.
Dipping is followed by blowing the extra slurry out of the channels, drying and

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calcination of the monolith. If the desired amount of the wash-coat (usually

20 wt%) is not reached the procedure is repeated.
Often wash-coating is non-uniform along the channel unless appropriate drying
methods are applied (Fig. 2.127).
Fig. 2.127: Photograph of the cross section of monolithic catalysts showing the impregnation
profiles obtained after static drying (left), freeze drying for 1 h, followed by static drying (center),
and freeze drying for 24 h (right). (Reproduced with permission from [66]).
In general, it can be stated that detailed information on the preparation of mono-

liths at the commercial scale is typically not released by the catalyst manufacturers
keeping it proprietary.
Metallic or ceramic foam are special types of structured catalysts with the ad-
vantages, that a shape required to fit the reactor size can easily be produced using
a template (Fig. 2.128).
Fig. 2.128: Metallic foams. (From [67].)
Ceramic foams have several other important advantages besides the ability to
match the shape and size of the reactor, such as much lower than packed beds’
pressure drop and much larger external surfaces allowing higher effectiveness

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factors and better heat transfer. The latter is important in avoiding local overheat-
ing and hot spots. Ceramic foam catalysts can be thus advantageous in case of
strongly exothermic or endothermic reactions. The open pore structure (Fig. 2.128)
can also help to control selectivity.
Lower solid loading when compared with packed beds (i.e., 10−20% vs 45−55%,
respectively) inevitably gives a lower productivity per reactor volume. This should be
compensated by better mass transfer within the catalyst layer, larger loading or even
more active catalytic phase.
Because of a more complex structure and a laborious procedure to prepare
foams discussed below, the costs of manufacturing foams are apparently higher
than that of more conventional catalyst shapes.
Complications in utilization of ceramic foam catalysts are related to their brittle
character and thus a potential breakage during manufacture and loading into a re-
actor. Moreover, long lengths of preformed ceramic foam might be troublesome to
charge in not perfectly straight reactor tubes.
Ceramic foams have lower pressure drop compared to packed beds, and com-
pared to conventional monoliths the flow pattern in gas–liquid system is closer to
that of packed beds.
Metallic foams could be either closed-cell or open-cell materials. The most com-
mon way to prepare closed-cell foams is to create gas bubbles in molten metal by
gas injection. Stabilization agents are introduced into the melt to prevent pore coa-
lescence. The size of the pores, or cells, is usually 1–8 mm. Open-celled metal
foams are usually replicas that use open-celled polyurethane foams as a skeleton
when first physical vapor deposition of metal is made onto reticulated polyurethane
foam followed by burn-off from the polymer foam.
Metal foams could be based on aluminum, nickel, chromium, iron or alloys.
Because of the large surface area, high thermal conductivity, mechanical durability
and corrosion resistance metal foams can be used as catalyst supports offering in-
creased heat and mass transfer and reduced diffusion resistance. Even if these ma-
terials have a potential to replace some conventional pellets or packing materials
the introduction of metallic foams into industry requires more quantitative data on
heat transfer coefficient, temperature profiles, stability and especially catalytic data
to support more widespread use of these foams.
Ceramic and carbon forms are also produced commercially. Mechanical strength
of these foams is lower compared to metal and cordierite monoliths. Polyurethane
foam templates with different pore size (Fig. 2.129) can be used for the preparation of
ceramic foams enabling unlimited shape and size combinations.
In order to prepare a ceramic foam block (Fig. 2.9) a defined piece of template is
dipped into the initial water solution, containing, for example, alumina as the main
compound and additives such as magnesia, titania and polyvinylalcohol. Uniform in-
filtration of the polymer by the aqueous slurry, composed of the ceramic particles
with the 0.1−10 μm diameter particles along with wetting agents, dispersion

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Fig. 2.129: Ceramic foams: polyurethane templates.
stabilizers and viscosity modifiers, is challenging. For better adherence, the polymer
foam might be pretreated (etched). Improved wettability needed for better quality of
the ceramic foam can be achieved by applying mechanical pressure or by vacuum
processing. Shear thinning of the fluid (i.e., the non-Newtonian behavior with viscos-
ity decreases under shear strain) is necessary for polymer template coating.
Low-viscosity suspensions are mainly used in dip coating and excess slurry is
removed by blowing air through the foam or by squeezing and kneading. The wet
foam is then dried and calcined in air at temperatures of 1,000−1,700 °C. Repeated
slurry coating is carried out with the green form for adjustment of the strut thick-
ness or filling cracks for crack filling or for functionalization of ceramic foams.
Recoating might be carried out with the so-called green foam prior to calcination or
after an intermediate sintering of the ceramic foam.
The laboratory-scale preparation procedure thus includes dipping, drying,
re-dipping, squeezing, centrifuging and air blowing followed by calcination of
the impregnated template. During the latter stage parameters such as ramping,
temperature and time are important in preparing the desired material. During the
calcination the template is burned and a replica of the template structure remains
consisting of α-Al2O3 and additives. Firing is a delicate process and can be accom-
panied by a foam block bending. The simplified scheme of the replica method for
synthesis of foams is presented in (Fig. 2.130).
The final steps in the preparation of the support are first wash-coating the foam
with a high surface area support material and then deposition of the active compo-
nent, which will be discussed in Section 2.3.6. The wash-coating of foams is princi-
pally made in the same way as the wash-coating for cordierite monoliths.
2.3.6 Supported catalysts
In supported catalysts, catalytically active compounds are attached to a support

with a large specific surface area. Industrial preparation of catalysts is considered
to be strategic and thus details of preparation are typically not disclosed or are

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Dispersion Foam template
Replication
Recoating Green-body
Burn out
Fig. 2.130: Processing scheme for foam

manufacturing (Reproduced with permission from
Sintering
[68]).
protected by patents. Patents typically feature broad claims and thus the exact
preparation procedures applied in industry are not revealed. Deposition of the pre-
cursor on the support surface can be done by using aqueous solutions and “wet”
methods of ion exchange, adsorption, precipitation and impregnation.
Alternatively, dry methods (i.e., atomic layer deposition) involving the gas-solid in-
terface could be applied. Initial deposition is followed by transformation of the pre-
cursor into the required active phase (metal, oxide, sulfide). An overview of the
methods applied for preparation of supported metals is given in Tab. 2.6.
Tab. 2.6: An overview of the methods for preparation of supported metals (Reproduced with
permission from [58]).
Synthesis method Metal Metal Advantage Challenge

loading dispersion
Colloidal synthesis Low–medium Medium Controlled size/ Anchoring on support

shape
Chemical vapor Low Monolayer Monolayer control Special equipment
deposition needed
Ion adsorption Low High Atomic dispersion Gradients over
support
Deposition High High–medium Reproducible Limited applicability
precipitation
Coprecipitation Very high Medium Very high Catalyst activation
loadings
Impregnation and High Medium Widely applicable Limited
drying reproducibility

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Placement of a support in contact with a solution containing a precursor leads

to electrostatic interactions, chemical binding to the surface and formation of sur-
face compounds. In addition, the support could undergo dissolution, at least
partially.
An ion exchange method involves the replacement of an ion in electrostatic con-
tact with the support by another ion. Because of the equilibrium nature of ion ex-
change a single operation might not be sufficient and several successive operations
should be adopted. Alternatively, the exchange solution is fed continuously through
the solid bed.
Adsorption of an active precursor on charged surfaces is typically done from liq-
uid and the precursor should be selected to have a charge opposite to that of the sup-
port. The latter depends on the isoelectric point of the oxide, pH and ionic strength of
the solution. The distribution of the active precursor depends on the density of the
adsorption sites on the surface, which is affected by the pH level. These methods in-
volve a subsequent washing step, contrary to impregnation, when a certain volume
of a precursor containing solution is put in contact with the support.
M M OH
M
O O OH
M M OH
OH M
O
OH OH
M M M
OH
O + H2O O + H2O
OH
M M M
OH
O OH
OH
M M M
OH
O O
OH
M M M
OH
O O
Fig. 2.131: Reaction of water with support hydroxyl groups.
2.3.6.1 Adsorption
Reaction of water with catalyst supports leads to hydroxylated surfaces (Fig. 2.131)
and formation of M–O− or M–OH2+ species.
The surface is thus charged depending on the solution pH. Surface charge is
equal to zero (isoelectric point or point of zero charge) at some particular value of
pH depending on the support pH. An increase in the pH levels results in the hydro-
lysis reaction of the surface OH groups shifting equilibrium from left to the right
hand side on Fig. 2.131. At a pH larger than the pzc the surface is negatively
charged, welcoming the adsorption of cations. For example, amine complexes
[Cu(NH3)4]2+ are very suitable for adsorption on silica at an elevated pH, when the
surface is negatively charged.

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The pzc of γ-alumina is between 7 and 9, so it can adsorb cations and anions.
Special care should be taken during catalyst preparation to the charge of the sur-
face and the charge of species to be deposited. For example, at low pH when the
alumina surface is positively charged platinum can be adsorbed from hexachloro-
platinic acid H2[PtCl6] as anions [PtCl6]2−. Fixation of anions on the surface is typi-
cally fast and does not limit the overall kinetics. In the case of platinum deposition
on alumina from H2[PtCl6], because of strong interactions between the complex and
the surface, platinum tends to adsorb strongly and rapidly, leading to heteroge-
neous distribution of the metal on the support. In order to avoid this, a competitor
(HCl) is added in industrial impregnations to ensure homogeneous distribution of
platinum. The conventional interpretation is that effective concentration of the plat-
inum precursor in the solution is influenced by the following equilibrium with Cl–
playing the key role:
½PtCl6 2 − =support + 2Cl − solution $ ½PtCl6 2 − =solution + 2Cl − support
An alternative explanation [69] assumes that the protons in HCl are needed to
charge the surface sufficiently for adsorption to occur.
In addition, HCl acts as a stabilizing agent for the coordination sphere of plati-
num, as otherwise [PtCl6]2− can lose several chloride ligands.
A successful recipe for one support will not necessarily work for another one.
Thus at pH 8 platinum could be adsorbed on silica from the cation using [Pt(NH3)4]
(NO3)2, while the same precursor will be inefficient for alumina (Fig. 2.132). Isoelectric
points of some typical supports are given in Tab. 2.7.
Adsorbed [Pt(NH3)4]2+
0.3
(mmol g–1)
Silica gel
0.2
0.1
γ-Alumina
0
6 7 8 9 10
pH
Fig. 2.132: Adsorption of [Pt(NH3)4]2+ from the solution on the surface of silica gel and γ-Al2O3.
(Redrawn from [70].).
The discussion above was mainly concerned with hydroxyl groups on the oxide
supports, however, the same careful attitude towards adsorption is valid for car-
bons supports, where the surfaces are also charged because of the presence of vari-
ous functions groups, such as carboxylic ones (Fig. 2.133). Thus H2[PtCl6] is used at

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Tab. 2.7: PZC of supports.
Support SiO CeO TiO FeO ZrO AlO ZnO CoO MgO
pzc    .–. . .– .– . .–.
Acidic groups
Lactol
Basic groups
O
Carboxyl Lactone O OH
O OH O O
Phenol Chromene
O Ketones
OH O O
Fig. 2.133: Functional groups on carbon support.
low pH on positively charged surfaces, while [Pt(NH3)4](NO3)2 should be applied at

high pH.
Point of zero charge of the support and pH are thus important parameters influ-
encing the electrostatic interactions between the metal complex and the support.
Regulation of pzc could be done by changing temperature (pzc is increasing for alu-
mina and decreasing for silica with temperature rise) and/or selective doping of the
support surface. In selective doping the dopant should not deactivate the catalyst.
As an example of selective doping, in alumina modifications with Mg+2 or F– ions
change pzc in the opposite directions. Even if pH is an important parameter, it
should be noted that measurements and control of pH are difficult tasks. Changes
in pH as mentioned above can cause dissolution of support and in addition can
change metal speciation, which leads to adsorption of other types of species. Such
changes in chemistry of adsorption should be thus taken into account during cata-
lyst preparation both at the experimental level influencing post-treatment and at
the theoretical level of modeling.
The type of ligand, in particular its charge and bulkiness, influences the nature
and the strength of the metal complex-support interactions. For example, shielding a
bulky ligand can decrease the interactions between the metal complex and the charged
surface. Moreover, a hydrated complex could be too large to enter the support pores.
Several metal precursors are suitable for catalyst synthesis. It should be noted
that metal salts (Tab. 2.8) are typically more expensive than the bulk metals. As
chloride containing precursors could suppress catalyst activity, thus nitrate

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precursors are applied or alternatively efficient washing methods should be used to

wash away chloride.
Tab. 2.8: Metal cations and anions used in catalyst

preparation.
Metal Anion Cation
Cobalt Co(NH)++
Nickel Ni(NH)++
Copper Cu(NH)++
Ruthenium Ru(NH)Cl++
Rhodium RhCl− Rh(NH)Cl++
Palladium PdCl− Pd(NH)++
Silver Ag(NH)++
Iridium IrCl− Ir(NH)Cl++
Platinum PtCl− Pt(NH)++
Gold AuCl−
In general, formation of different species with different charges should be modeled

as a function of pH and other concentrations (Fig. 2.134). The surface ionization re-
actions are described by two constants (Fig. 2.135), which along with the surface
density of hydroxyls and the dielectric constant, characterize the charging proper-
ties of an oxide defined through pzc = [0.5 (pK1 + pK2)].
–
HO HO O
+
H C C C
O O O
pH < PZC < pH
Fig. 2.134: Surface charge dependence on pH for carbon supports with carboxylic groups.
In order to model adsorption behavior (Kads) a simple Langmuir type adsorption

model for the metal adsorption capacity is often applied
cp K
a = a∞ (2:37)
cp K + 1
where cp is equilibrium concentration, K is adsorption equilibrium constant and a∞

is maximum sorption capacity. As a typical example, adsorption isotherms of
H2PtCl6 on carbons are presented in Fig. 2.136.
Adsorption models available in the literature very seldom consider lateral inter-
actions between adsorbed ions, site heterogeneity and oxide dissolution. Such dis-
solution could occur when deposition of the active agent happens at a pH far from

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Kads, anion
OH2+ [PtCl6]2–
pH < PZC
K1
(pH shift)
PZC OH [H]+
K2
Kads, cation
pH > PZC O– [(NH3)4Pt]2+
Fig. 2.135: A schematic presentation of the mechanism of electrostatic adsorption of platinum.

(From [71].)
CG-48A
Active carbon
1
Sibunit
Ptads (mmol g–1)
Pyrocarbon
0.5
Mogul L
Coke
0
0 0.05 0.1
Equilibrium Pt concentration
in solution (mol L–1)
Fig. 2.136: Adsorption isotherms of hexachloroplatinic acids on carbon (From [50]).
the pzc of the support, i.e. the point of maximal stability of the solid because of
minimum solubility.
Dissolution of the support could also be beneficial to a certain extent. New
hydroxyl groups created because of silica dissolution in a basic medium act as ad-
sorption sites, resulting in an increase of cations adsorption on silica at pH higher
than 10.5.
It should be noted that not only the desired ion but also the associated counter-
ion could interact with the support. Moreover, the counter ions can determine the
precursor solubility.
2.3.6.2 Impregnation and drying

Impregnation, which is in a way similar to adsorption, could be done by contact-
ing a certain volume of solution with a precursor and the support (Fig. 2.76). The

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method is used to obtain higher loading than in simple adsorption and to apply
active precursors that do not adsorb easily on support. In this preparation method
the solution of the precursor is broken down into small discontinuous elements
presented in the pore of the support by gradually evaporating the solvent. The
wetting time could be modified by changing the temperature of impregnation,
which has an influence not only on pzc but also on the precursor solubility and
viscosity of the solution. Mass transfer of the impregnated compound within the
pores during impregnation and drying determines the concentration profiles.
Solubility of the precursor in the solution limits the maximum loading, thus suc-
cessive impregnations with drying and even calcinations between these impreg-
nations are applied to increase the loading, as will be discussed separately in
Section 2.3.6.3.
In wet impregnation an excess of solution is used and after a certain time the
solid is separated and the excess solvent is removed by drying. In this non-
exothermal method the pores are filled with the neat solvent prior to impregnation.
When this solvent saturated support is introduced into the solution containing the
precursor there is a concentration gradient between the external solution and the
pores driving the precursor salt in the pores.
In dry methods (pore volume impregnation or incipient wetness) the volume of
the solution containing the precursor corresponds exactly or approximately to the
volume of the pores. One of the disadvantages of the method is broad particle size
distribution. If pH is not adjusted and, for example, impregnation is done at condi-
tions when pH is close to pzc, only few hydroxyl groups are available and non-
adsorbing metal particles might agglomerate giving large crystallites.
In dry methods a replacement of the solid-gas interface by a solid liquid one
causes a significant decrease in the free enthalpy. This results in heat release,
which in general is of minor importance for impregnation. In some special cases
this heat release might influence impregnation by provoking unwanted precipita-
tion, limiting solubility or modifying the surface.
When solution is sucked into pores by capillary forces, air bubbles are trapped
and could burst the support and lower the mechanical strength. This is caused by
considerable forces exerted on the pore walls being in contact with these bubbles
during dry impregnation. The reason is in the high pressure (several MPa) inside
the compressed bubbles defined by the Young-Laplace law:
2γ
ΔP = (2:38)
r
where ΔP is the pressure difference inside and outside the bubbles, γ is the liquid-
gas interfacial tension and r is the liquid-gas meniscus radius.
In order to prevent or limit the bursting of the support during impregnation, a
surfactant could be added to the solution or impregnation could be done in vac-
uum, complicating the whole procedure.

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Time needed for the liquid to fill the pores is very short (a few seconds) in dry
impregnation, although in practice longer operation times are used. Contrary to
capillary impregnation in wet methods (diffusional impregnation) migration of the
precursor into the pores is much longer and distribution of the solute is governed
by diffusion into the pores (Fick law can be applied) and adsorption on the support
(typically Langmuir model is used). As already mentioned above, adsorption de-
pends on the adsorption capacity and the equilibrium constant of adsorption.
Phenomena during wet and dry impregnation are illustrated in Fig. 2.137. The
characteristic time t needed to attain equilibrium in wet impregnation is propor-
tional to the square of a pellet radius, thus is increasing with the pellet size and is
far from instantaneous but requires several hours.
Adsorption Adsorption
Air
Dissolution
Diffusion Diffusion
Capillary flow
Solute Solvent Support
Fig. 2.137: Phenomena of transport involved in (left) wet impregnation and (right) dry impregnation.
The solute migrates into the pore from the left to the right of the figures. (Redrawn from [72]).
In dry impregnation pressure-driven capillary flow of the solution inside the empty
pores is described by the Darcy’s law:
KKl, eff
Nl, s = − Cl, s ΔPl (2:39)
ηl
where Kl,eff is the relative permeability of the liquid-phase, η is its viscosity, K the
intrinsic permeability, and Pl is the liquid-phase pressure that is equal to the local
gas pressure minus the capillary pressure PC. Influence of viscosity and concentra-
tion on the diffusion is complex. High viscosity associated with high concentra-
tions prevents the precursor diffusion according to eq. (2.39), while at the same
time a high concentration favors the diffusion of the solute toward the center of
the pellet.
Quantification of the conditions leading to profiling during adsorption and im-
pregnation can be done by considering the characteristic time tC at which the solu-
tion completely fills the pore volume:

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8r2 η
tC = (2:40)
rC γ cos θ
where r is the grain radius, θ is the wetting angle, γ is the liquid-gas interfacial ten-
sion, η is the liquid viscosity, rc is the pore radius. Uniform distribution can be
achieved when the impregnation time is a priori longer than the time tc of capillary
impregnation. Otherwise distribution will be non-uniform.
For wet impregnation the characteristic impregnation time tD is given by:
r2 ð1 + PÞτ
tD = (2:41)
DM ε
where τ is the pore tortuosity, DM is the molecular diffusion coefficient of a compo-
nent in the solution, τ is the porosity and P is the ratio between adsorbed and non-
adsorbed amounts of the deposited compound in the support volume, i.e.,:
a
P= (2:42)
g−a
In eq. (2.42) a is the amount of a compound adsorbed and g is the overall amount of
this compound located in the pores (trapped or adsorbed). When P > 1 the precursor
is mainly adsorbed and the metal deposition can be defined as adsorption, while at
P < 1 the role of adsorption is much less prominent. In practice contribution of ad-
sorption and impregnation is comparable.
Uniform distribution is achieved when the impregnation time is substantially
larger than the characteristic impregnation time tD, which as follows from eq. (2.41)
depends at P << 1 on the grain radius, pore structure and diffusion coefficient.
When P >> 1 the overall process might be limited by adsorption. For strongly ad-
sorbing compounds the characteristic impregnation time could be so high that uni-
form distribution cannot be reached.
Otherwise, for weakly adsorbing compounds long impregnation times will lead
to uniform distribution (Fig. 2.138). Such distribution is needed for slow reactions
occurring in the kinetic regime without diffusional limitations.
Impregnation time increases
Active phase Support
Fig. 2.138: Influence of impregnation time on active phase profile.

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Increase of the precursor concentration in principle increases the penetration

depth and leads to more uniform distribution. This approach is not, however, very
efficient as it gives low P values and requires unnecessary high quantities of the
active compound.
Another option to improve uniformity of the active phase profiling is to dimin-
ish the grain size, which obviously has technical limitations because of other re-
quirements such as pressure drop in the reactor. Uniform precursor distribution is
also achieved when precursors and competitors (HCl or acetic acid) are equally in-
teracting with the surface.
Finally, temperature of impregnation is usually of minor importance regarding
precursor distribution.
Egg-shell distribution is applied for diffusional limited reactions when the inter-
nal part of a grain is not utilized in catalysis. In general, in order to get an egg-shell
distribution, one of the options is to use a precursor, which should be strongly ad-
sorbed during impregnation. Impregnation with a very viscous solution can be rec-
ommended as an alternative technique.
An interesting option is egg-yolk distribution, when the active phase is concen-
trated in the center of the grain. Such distribution is obtained when there is a com-
petitor interacting more strongly with the surface than the precursor. It could be
useful for slow reactions when the particles undergo severe attrition. For example,
synthesis of platinum on alumina catalysts could be considered with hexachloro-
platinic acid as a precursor. In the presence of oxalic or citric acids, which adsorb
stronger than the platinum precursor, adsorption of H2[PtCl6] at the outer layer is
prevented, forcing it to move further towards the grain center.
Finally an egg-white distribution with the location of the active phase away
from the outer surface and the center can be used when the center of the grain is
not used because of diffusional limitations, while the outer surface without the
active phase is needed to protect the catalyst because of attrition or poisoning.
Such distribution could be achieved by, for example, using oxalic acid prior to im-
pregnation and then regulating the concentration of competitor and impregnation
time.
Elimination of the solvent after impregnation is done by drying, or in other
words heating the solvent up to the boiling point under static conditions. Uniformity
of distribution depends not only on impregnation but also on drying. When adsorp-
tion is weak or moderate it is intuitively expected that the metal profile in the pellet
can change during drying. To prevent migration of the weakly interacting precursor,
drying can be done at room temperature. An alternative method is to dry a concen-
trated, viscous solution obtained by addition of cellulose derivatives.
Although drying chemistry is typically not considered in modeling of impregna-
tion, it might be important in influencing the after-drying steps. For example, plati-
num complexes adsorbed on the oxide surface undergo further transformations at
the drying stage. When high loaded [PtCl6]2− on alumina is dried at room

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temperature two chloro-ligands are replaced by the two hydroxyl groups of the sup-
port, changing the complex-support bonding. When dried at higher temperatures
the hydrolyzed platinum complexes could lead to polynuclear hydroxo complexes,
which require reduction at higher temperatures.
Changes in the heating rates also govern drying and can lead to non-uniform dis-
tribution. The slow and fast drying regimes are presented in Fig. 2.139A. Compared
with slow drying, fast drying, usually associated with high heating rate and drying
temperature, tends to block all movements of the solute toward the outside of the
pellet.
Micro-
Adsorption convection Adsorption
Back-diffusion Evaporation
Back-diffusion Evaporation
Convection Convection
Solute Solvent Support

(A)
100
Uniform
DI,i × 1010 (m2 s–1)
Egg-shell
10
Pronounced egg-shell
1
50 100 150 200 250 300
(B) T (°C)
Fig. 2.139: (A) Phenomena of transport involved in (left) slow and (right) fast drying. The solvent
migrates from the left to the right of the figures. Microconvection is not mentioned on the right
side for the sake of clarity. (Redrawn from [73].) (B) Contour map of the final metal profile in the
diffusion coefficient – drying temperature plane. (Reproduced with permission from [73]).
During drying the reactions between the precursor and the support could be non-
uniform because of different solvent (water) amounts and non-isothermicity along
the pore leading to a position-dependent particle size distribution.
It is apparently clear from the discussion above that impregnation is a complex
process depending on a number of interrelated parameters (concentrations, pH, viscos-
ity, presence of counterions and competitors, solvent). As operational parameters, pH
adjustment, introduction of ligands or organic additives and impregnation duration
could be used. In the drying step temperature, heating rate, gas flow and pressure, as
well as drying time could be also altered to influence the resulting supported catalyst.

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Because of the complexity of impregnation, which should be considered to-

gether with drying, only a few studies have been conducted with a detailed engi-
neering analysis. As an example of an engineering approach to study impregnation
and drying, the work on parametric investigation of impregnation and drying of
supported catalysts by Liu et al. [73] should be mentioned. For drying, the mass bal-
ances of the drying medium (air) and the solvent (water) were considered in addi-
tion to metal dissolved in the liquid and adsorbed on the support. Simulations for
the case of drying with uniform initial conditions demonstrated that the effective
diffusion coefficient and the drying temperature have the most significant impact
on the metal redistribution during drying. The most pronounced egg-shell profile
can be observed at the point of the highest drying temperature and the smallest ef-
fective diffusion coefficient (Fig. 2.139B).
The rate of drying also influences the profile of the active phase (Fig. 2.140).
Thus egg-shell profiles can be enhanced by increasing the drying rate.
Increasing rate of drying
Catalyst
particle
Egg-yolk Homogeneous Egg-shell
Fig. 2.140: Influence of the drying rate on the active phase profile. (Redrawn from [74]).
2.3.6.3 Multiple adsorption and impregnation

As the required amount of the active precursor cannot necessarily be dissolved in a
liquid volume used in pore volume impregnation, high metal loadings could not be
always achieved and multiple impregnations are needed.
Let us first analyze the mass balance for impregnation following the treatment
presented by Pakhomov [50]. The initial amount of the active component precursor
G0 can be calculated as:
G0 = V0 c0 (2:43)
where V0 is the initial volume of the solution with concentration c0.

After the impregnation time τ a certain amount of the precursor g is trapped in
the pores of the volume VΣ and the concentration of the precursor in the solution
changes to cτ . Thus:
Gτ = g + ðV0 − VΣ Þcτ (2:44)

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For wet impregnation in the diffusional regime and combining eqns. (2.43) and
(2.44) one gets an expression for g:
n
g = VΣ c0 (2:45)
n+1
where n = V0 =VΣ is the excess of the impregnation solution compared to the pore
volume. For dry impregnation:
g = VΣ c0 (2:46)
The maximal amount of the active compound that could be loaded on the support
during one impregnation is determined by pore volume VΣ and the solubility cs of
the precursor:
g = VΣ cs (2:47)
Multiple impregnations are usually needed when the desired amount of the active
compound is rather high (above 20 wt%).
It should be noted that since the amount of the available pore volume is re-
lated to the volume of the precursor (bulky organic salts or hydrates), this vol-
ume could be already filled after the first impregnation, while the amount of the
active compound is below the requirement. In such cases thermal treatment is
needed between subsequent impregnation steps to form an intermediate (for ex-
ample, oxides from metal salts). Obviously, as multiple impregnations compli-
cate catalyst preparation, the number of impregnations should be as small as
possible.
Volume of either the intermediate compound or the metal after the first impreg-
nation (followed by thermal treatment) is:
g1M g1A M
ΔV = = = g1 α (2:48)
ρ ρ A
ρ is density, A/M is metal content in intermediate, A is metal mass, M is mass of the

intermediate, g1M or g1A is mass of intermediate or metal after first impregnation
and α = M/Ap.
Free volume of pores after the first impregnation is given by
V1 = V0 − ΔV = V0 − g1 α = V0 ð1 − c0 αÞ (2:49)
Free volume after i impregnation for uniform distribution and no pore blockage can
be expressed in the following way
Vi = V0 ð1 − c0 αÞi = V0 − gα (2:50)
The value of α could be easily calculated for the intermediate compounds when
density is known or experimentally determined through estimation of the pore

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volumes after impregnations. When α is known all the required parameters to per-
form multiple impregnations could be calculated, such as the number of impregna-
tions i needed to introduce g grams of metal per gram of support at c0:

lg 1 − Vgα
0
i= (2:51)
lgð1 − c0 αÞ
the amount of metal g loaded in i impregnations:
ð1 − αc0 Þi − 1
g = V0 − (2:52)
α
the volume of solution needed for i impregnations:
X
i−1
Vp = V0 ð1 − c0 aÞi − 1 (2:53)
1
and the minimum volume of pores needed to introduce the needed amount of metal g:
gα
V0, min = (2:54)
1 − ð1 − c0 αÞi
2.3.6.4 Industrial implementation of impregnation

Industrial-scale impregnation is done in both common type reactors and in dedi-
cated equipment. The conveyor type of wet impregnation equipment (Fig. 2.141) has
been used for large-scale impregnation. Conceptually, in this method the catalyst is
loaded in buckets that are moving down into the impregnation basin. The impreg-
nation time depends on the conveyor speed and the length of the basin. The con-
centration of the impregnation solution is kept constant.
For dry impregnation the impregnating solution is sprayed over the support
(Fig. 2.142), which is rotating.
(A) (B)
Fig. 2.141: Conveyor wet impregnation. (A), from [75], (B) from [48]. Explanations are given in the
text.

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Impregnating solution
Spray header
Support to be
impregnated
Rotating drum
Fig. 2.142: Incipient wetness impregnation. (Redrawn from [38].)
There are also reactors operating batch-wise, which allow impregnation and
drying and calcination in the same reactor. The reactor with the volume of 0.25–10
m3 can have a capacity of 100–2,000 kg/day, operating with air as a drying and
calcination agent at, respectively, 80–180 °C and up to 600 °C. An example of syn-
thesis of zinc acetate on a carbon support is illustrated in Fig. 2.143. Activated car-
bon is charged through the pipe pos. 1. For a reactor diameter of 2 m, the height of
the support bed is approximately 0.6–0.7 m. Prior to impregnation, the support is
dried by air through the distribution grid 4. The bed is fluidized by adding
Steam air mixture
Support
2 Impregnating solution
6
3
4
Steam 5 Impregnated support
Air
Fig. 2.143: Reactor combining impregnation, drying and calcination [48]. 1, pneumatic tube for
loading the support; 2, heating elements; 3, fluidized bed of the support; 4, distribution grid;
5, discharging outlet; 6, spraying.

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approximately 20–30% more air than the fluidization threshold. After drying of the
support, the solution of zinc acetate is sprayed through distributer (pos. 6).
Intensive mixing guarantees efficient impregnation. Air steam mixture containing
dust is taken from the reactor top. Reactor is heated by steam through spiral ele-
ments pos. 2. After impregnation in the same reactor, the catalyst is matured, dried
in air at 70–110 °C and unloaded through pos. 5.
This reactor operates batch-wise. To enhance throughput, two reactors for im-
pregnation can be employed (Fig. 2.144), one undergoing impregnation while the
support is unloaded from the second one.
Fig. 2.144: An installation with two reactors for impregnation [76].
As an example, for catalyst preparation by impregnation, a supported silver catalyst

for synthesis of formaldehyde by oxidation of methanol will be discussed. The syn-
thesis of formaldehyde can be performed in a fixed-bed reactor with silver catalysts.
The global production of formaldehyde is divided by this process and alternative
oxidative dehydrogenation at a lower temperature on Fe–Mo oxide. More details
are provided in chapter 4. Because the methanol and air mixture is flammable, a
safe process should operate either below or above the flammability limits (6.
7–36.5% methanol in dry air at 100 °C). Oxidative dehydrogenation of methanol on
silver is organized above the higher limit at 600–700 °C, allowing to achieve the
yields of formaldehyde exceeding 85%.
The classical method of catalyst preparation by impregnation developed in the
1950s is still used, although at the beginning of the twenty-first century an

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alternative electrolytic preparation method was commercialized based on the dis-

covery that the crystal growth could be controlled by the creation of a silver-
diamine complex during the electrochemical synthesis step.
In the classical method silver (30–35 wt%) on pumice is prepared by impregna-
tion of pumice by silver nitrate (Fig. 2.145).
HNO3
AgNO3 NO, NO2

1
2 3 8
Catalyst
2
4
5 6 7
Fig. 2.145: Preparation of silver catalyst by impregnation, 1 – grinding, 2 – sieving, 3 and 6 reactors
with impeller and heating jackets. 4 – filter, 5 – dryer, 7 – calcination. (Redrawn from [48].)
The large grains of the support are ground (pos.1) and sieved (pos.2). The smaller and
larger fractions are disposed and returned to grinding, respectively, while the me-
dium fraction (2–5 mm) is introduced in the reactor with a heating jacket (pos. 3).
Nitric acid is added into the reactor 3 at 60–70 °C for 7–8 h order to remove iron con-
taining impurities
Fe2 O3 + 6HNO3 = FeðNO3 Þ3 + 3H2 O
FeO + 6HNO3 = FeðNO3 Þ2 + H2 O
that otherwise lead to cracking and coking.

After filtering out and washing with water the support is dried at 100–110 °C and
then impregnated in another reactor (pos. 6) with a solution of silver nitrate, with si-
multaneous evaporation of water at 100 °C. After impregnation that results in deposi-
tion of silver mainly in the pore mouth and on the external surface, the catalyst is first
thermally treated at 400–500 °C for 1–2 h to remove NOx followed by calcination at
approximately 650 for 2–3 h. The level of NOx emissions is approximately 0.4 ton per 1
ton of catalyst, while an approximate feedstock consumption for production of 1 ton
of silver on pumice catalyst is as follows: pumice – 630 kg, nitric acid (47%) – 800 kg,
hydrochloric acid – 475 kg, silver nitrate – 740 kg. The example above has mainly ed-
ucational purposes as in industrial practice mainly silver gauze’s are applied.
2.3.6.5 Precipitation
This method has two main variants. The first one is used when cheap catalysts
are produced and the aim is to optimize the activity per volume unit. It relies on

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co-precipitation of the support and the active component which gives a material
that is then dried, calcined and if needed reduced. Details of this method are
covered in a section devoted to the precipitation of bulk oxides (Section 2.3.3),
as the CuZnOA2O3 (Fig. 2.95) catalyst described in that section can be also con-
sidered as copper and zinc oxide supported on alumina. Precipitation is caused
by adding a precipitation agent such as sodium hydroxide or bicarbonate.
A short description of the nucleation phenomena was provided in Section 2.3.3.
Thermodynamic analysis of deposition-precipitation should also consider the inter-
facial energy with the support. Because of the presence of such interactions the
total free energy also includes enthalpy of the support-nanoparticles (NP) interface:
ΔGtotal = ΔHNP + ΔH NP − TΔS (2:55)

sup
and can be significantly lowered. This in turn results in a lower concentration of the
active precursor at which the crystallization rate can be measured. Solubility plots in-
cluding the solubility and supersolubility curves are presented in Fig. 2.92. The solubil-
ity curve (saturation concentration) separates liquid from the solid, indicating that
solubility increases with temperature. There is a concentration (supersolubility, or nu-
cleation threshold) where the precipitation becomes abruptly measurable. Between
these two lines of solubility and supersolubility precipitation does not occur within the
bulk and happens exclusively on the support. Keeping the concentration of the catalyt-
ically active precursor in this range is the basis of the deposition-precipitation method.
This second method of precipitation, originally developed for high loading of
the active phase, employs pre-existing supports and is preferred when the active
phase precursors are expensive and deposition of a nm size active phase is needed.
Obviously, precipitation in the bulk should be avoided. As mentioned above, metal
hydroxides or carbonates precipitate on the support after the addition of a base to
increase pH.
In order to achieve homogeneous precipitation, pH should be homogeneous
(difficult to achieve during scaling up) and the concentration of the active precursor
should be below the supersolubility curves.
Such homogeneous solution can be obtained in the case of deposition-
precipitation with urea that slowly hydrolyzes at 70–90 °C according to the follow-
ing reactions:
ðNH2 Þ2 CO = NH4+ + CNO − ;
CNO − + 3H2 O = NH4+ + HCO − + OH − ;
CNO − + 2H2 O = NH4+ + CO2 + 2OH − .
The rate of urea hydrolysis does not depend on pH as it is of first-order towards

urea. The amount of urea is typically 1.5–2.5 times above stoichiometric because of
ammonia volatilization.

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It should be also mentioned that although urea hydrolysis takes a relatively

long time there is a possibility to thoroughly mix the support suspension at a tem-
perature where there is no reaction. This allows for preparing highly concentrated
solutions. Large amounts of highly viscous suspensions of support can therefore
be used with urea, separating the mixing of the ingredients for catalyst production
and the generation of precipitating agents. This is especially important for the
scaling up of catalyst preparation as efficient stirring is difficult to achieve in
large vessels.
Deposition-precipitation with urea gives a constant level of supersaturation by
maintaining a uniform concentration of OH– in both the bulk and pore solutions.
The precipitated phase is a hydroxide of the active metal. Supported Mb, V, Fe, Ni,
Cu and gold catalysts could be prepared by deposition-precipitation with urea.
The drawbacks of the method are the possible formations of cyanate and nitrite
in the waste water and release of NO.
Obviously, properties of the support are important in the deposition-precipitation
process. Thus, large particles could be formed in the case of neutral support surfaces
close to the support pzc, neutral metal complexes, lack of hydroxyl groups on the
support surface at low pH or dissolution of the support at low pH. In addition, the
following lead to large particles: the repulsions occurring between the anion and
the negatively charged, deprotonated support surface at pH above the pzc of the sup-
port, the presence of chloride causing agglomeration of metal particles, low stability
and slow adsorption rates of some metal complexes, such as Al(OH)4–.
Besides the strength of interactions between the metal precursor and the sup-
port, maturation time and redispersion also have an impact on the final nanoparti-
cle size.
Changing the pH level of a solution of an active precursor, changing the va-
lency of a dissolved active precursor, or decreasing the concentration of a com-
pound forming soluble complexes with the active precursor are procedures that can
be used in deposition-precipitation. Many deposition-precipitation procedures in-
volve an increase in the pH level of a suspension of the support in a solution of the
active precursor. As a significant number of catalytically important metal com-
pounds dissolve as oxy-anions, raising the pH level cannot be used to bring about
the precipitation of such metal ions, and consequently a procedure has been devel-
oped to reduce the metal in the oxy-anions to a lower valency. The metal ions of a
lower valency exhibit a basic behavior and are thus soluble at low pH levels and
precipitate at high pH levels.
For the supports with high pzc the use of the deposition-precipitation (DP)
method is challenging. The DP method is also not very easy to perform for hydropho-
bic carbon. As the nature of adsorption sites for oxides and for carbon is different,
the same method of pH adjustment cannot always be applied. Zero potential of silica
does not change when increasing the pH from 3 to 7, whereas these changes are sig-
nificant for carbon in the range of pH 2–5. Carbon surface is thus oxidized to

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efficiently increase the number of carboxylic groups and subsequently the loading. A
particular case is preparation of carbon supported gold catalysts, which could be eas-
ily reduced during deposition, leading to large clusters of gold. In order to avoid it,
gold colloidal sols are prepared with polyvinyl alcohol (PVA) followed by a reduction
with NaBH4, drying, and finally deposition onto the carbon support.
A simple thermodynamic model [77] that takes into account the number of hy-
droxyl groups on oxide surfaces during the preparation of supported catalyst par-
ticles by deposition-precipitation with urea assumes that the interfacial energy can
be represented by two terms:
ðpH − pzcÞ
γss = γ0SS + γelectrostatic
SS = γ0SS + γ0SS λ (2:56)
pzc
one γ0SS describing pH independent non-electrostatic interfacial energy, while the

other γelectrostatic
SS denotes electrostatic energy between a nanocluster and the charged
surface.
The latter is proportional (with λ being the cluster size independent propor-
tionality constant) to the relative approach of pH to the point zero charge
Δz = ðpH − pzcÞ=pzc. The latter parameter could be either positive or negative (for
example, for supports with high pzc, such as magnesia). This simple approach al-
lows for predicting dependence of the cluster size on the pH at which precipita-
tion was performed. The enthalpy for nanoparticles is a function of the number of
nanoparticles multiplied by the surface free energy and the atomic volume of bulk
metal. The number of nanoparticles for a hemispherical cluster can be written as
a cubical equation with respect to the particle radius r. The minimal total energy
with respect to this radius can be derived by taking into account the above men-
ΔGtotal
tioned correlations via taking a derivative = 0 giving finally:
dr
p2 p2
r3 − r− =0 (2:57)
Δz Δz
With:
ðβRT − γ0SS Þ 4αγΩ

p1 = 3 , p2 = − 2 0 (2:58)
γ0SS πλ γSS πλ
where α is a dimensionless coefficient of an order of unity (α can be equal to 1 only

for spherical particles), Ω is the atomic volume of the bulk metal, R is the gas con-
stant, β is a dimensionless constant (β≈ 5–8). Despite the apparent simplicity of
eq. (2.57), modeling of the cluster size dependence as a function of Δz (Fig. 2.146)
shows clearly that the proposed model can be used as a tool for the estimation of
the metal particle size on a given support surface.

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1.8
1.7
Cluster radius (nm)
1.6
1.5
1.4
1.3
1.2
1.1
1.0
0.0 0.1 0.2
Δz
Fig. 2.146: Dependence of cluster radius on Δz for gold catalysts on titania prepared by deposition-
precipitation with urea at different pH. (Redrawn from [77].)
2.3.6.6 Atomic layer deposition

Dry methods of catalyst preparation, such as chemical vapour deposition (CVD)
and atomic layer deposition (ALD), being inherently more expensive than wet meth-
ods, have their advantages resulting in catalysts with controlled metal dispersion.
In fact the dispersion could be very high at significant loadings. In CVD, volatile
precursors are deposited in a “cold zone” directly from the gas-phase and thin films
are formed on the support surface by thermal decomposition or reactions of gas
compounds.
ALD uses alternating cycles of self-limiting reactions and deposition occurs in a
layer-by-layer fashion. Sequential exposure of the support with surface hydroxyl
groups to, for example, trimethyl aluminum Al(CH3)3 and water, results first in the
formation of O-Al linkages and the generation of methane in the gas-phase
(Fig. 2.147). When no surface hydroxyl groups are available the reaction terminates.
The surface methyl groups can react, however, with water producing methane and
another set of O-Al linkages.
Typically a constant stream of an inert gas (N2) is flowing through a chamber at
a pressure of ~0.1–10 Torr and the precursor vapors are injected into this carrier
gas. A purge period is introduced between each precursor dose to avoid mixing of
the chemicals, which can give non-self-limited growth. The film thickness is very
precisely controlled by the number of precursor cycles rather than the deposition
time, as is the case for conventional CVD processes.
For growing thin films, reaction cycles with the metal and the non-metal reactants
require just seconds being performed at the same temperature. For porous materials,
longer reactant exposures (hours) are needed. Moreover, longer times allow different
reaction temperatures to be used for the two reactants. Organometallic compounds
and metal halides are most commonly applied as metal reactants. The deposition of
noble metals by ALD requires a long time because of the difficulties in removing the

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Gas in
A CH4 Coil
CH3 H3C CH3 power
Al(CH3)3 Al Al
OH OH OH O O O
Inert gas
Substrate Substrate valve
Precursor
in
B CH4
CH3 H3C CH3 OH HO OH
Al Al H2O Al Al
O O O O O O
Substrate Substrate
Table
(A) (B) Pumps power
Fig. 2.147: Illustration of surface chemistry for alumina ALD. (A) (From [78]), (B) Figure courtesy of [79].
ligands from the noble metal precursor bound to an oxide surface. Poor nucleation and
the ability of noble metal atoms to agglomerate results in the formation of highly dis-
persed metal clusters of nanometer size.
Desirable characteristics for ALD precursors include high volatility, good ther-
mal stability at the ALD growth temperatures, and high reactivity with the other
compound used for the film growth.
2.3.7 Catalyst forming operations
Several post-treatment and forming operations, which are performed during cata-
lyst preparation, were briefly discussed in Section 2.3.1.2. Catalyst forming, which is
seldom considered in academic research, is, however, extremely important for the
preparation of catalysts influencing the final performance. Information about cata-
lyst forming is typically proprietary and primarily empirical. Only a few reviews on
catalyst forming are available, such as Schüth and Hesse [80]. At the same time, it
is apparently clear that solid engineering approaches are needed in this field, other-
wise unit operations in catalyst preparation will resemble those used centuries ago
(Fig. 2.148).
Spray-drying, extrusion, pelleting and granulation are the most important cata-
lyst forming methods to give different catalyst shapes, which define the pressure
drop in a reactor. The properties of a primary solid in terms of activity and selectiv-
ity should be maintained. In addition to the primary porosity, compaction creates
additional porosity that is important for mass transfer. Porogenes are added during
forming, and are burned when the catalyst is calcined. These porogens that help to

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Fig. 2.148: Unit operations. (A) Georg Bauer (Agricola), “De Re Metallica” (1566). (B, C) Catalyst
preparation operations. Photo courtesy of Dr. I. Simakova.
improve porosity could have adverse effects. The distribution of particle size in the
powder that is used for compaction can be beneficial, as the fines fill the voids and,
after agglomeration, improve the strength of the large particles. Mixing the particles
with different sizes could be challenging as they tend to be accumulated in different
parts of a reactor (smaller at the top). Moreover, in some cases excessive fine pow-
der leads to pilling problems.
Forces of varying strength ranging from weak and medium (van der Waals,
electrostatic, capillary forces) to strong bonds (covalent, siloxane bridges) are in-
volved in the agglomeration of solid particles. Even the weak van der Waals forces
of very small particles could be of importance when dispersion forces are prominent
for many points of contacts between particles.
2.3.7.1 Spray-drying
Spray drying is a method for producing attrition-resistant microspherical catalyst
particles. In the spray dryer, the slurry comprising the catalyst particles, suspended
in an aqueous sol or hydrogel of a binder (e.g., silica–alumina, alumina, clays), is
sprayed into a hot gas flow. The binders are used if shaping is otherwise not possi-
ble in the spray-drying process.
Spray-drying can be used to generate the catalysts in the final shape or
make powders that will be further processed with another method. Spray-drying
process results in 10–100 μm of almost identical shape particles, which could be
used in processes operating in fluidized bed reactors, such as fluidized catalytic
cracking.
During spray-drying a powder slurry in water suspension (10–30 wt%), prepared
by milling (for example, the filter cake to the size of several hundred nanometers), is
fed through a nozzle that sprays small droplets into hot air. The formation of micro-
spheres occurs when the spray falls downward in the dryer, the binder particles

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undergo gelation and the solvent evaporates. This results in embedding of the cata-
lyst particles into a matrix of cross-linked particles.
In high gas temperatures calcination can even occur. This process can be re-
peated, that is, spray-dried particles can be processed the second time to furnish
them with a protective shell.
The nozzle (or atomizer) generating the spray is very important in spray-drying,
defining the diameter and size distribution of the droplets. The choice of the spray
nozzle construction material is important, especially in the presence of abrasive
components in the slurry.
Rotary atomizers with a hollow wheel rotate at high speed (up to 20,000
revolutions min−1) to spray the slurry mechanically which leads to fine to medium
coarse powders. Another parameter is the flow direction, which could be cocurrent,
counter-current, or a mixed flow. The air distribution is needed to ensure homoge-
neous flow across the chamber. In a cocurrent operation mode the hottest air con-
tacts the droplets at a stage when the majority of the water is still present, giving
the most desired profile.
The particle size distribution is adjusted through control of the atomizer wheel
speed. Coarse grained powders can be produced using a low speed atomizer wheel
operation.
For conditions when the inlet drying temperature is restricted to below 550 °C,
roof air dispersers are used (Fig. 2.149). When high outlet temperatures are needed,
part of the exhaust air can be recycled to preheat the drying air passing to the dry-
ing chamber, improving the overall heat efficiency.
Catalyst formulations containing organic solvents are dried in an inert gas
closed cycle plants.
Feed
Drying air
Product
Fig. 2.149: Spray dryer with a rotary atomizer and a roof air disperser. (From [81].)

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There are several advantages of rotary atomizers, such as rather narrow par-
ticle size distributions, requirements of high-pressure pumps only when very
thick pastes are sprayed, resistance to plugging, ability to handle relatively abra-
sive slurries, and high capacities. The design is, however, more mechanically de-
manding and the size of the catalyst particles is tightly bound to the diameter of
the drying chamber. Dependence of the mean particle size as a function of the
chamber diameter is discussed by Roberie et al. [82] and demonstrates that,
for example, FCC catalysts (65–80 μm) require a particular chamber diameter
(2.8–4 m).
2.3.7.2 Size reduction and granulation

Both types of operation (size reduction and size enlargement) are used in catalyst
preparation.
Ball mills and agitated media mills can be used to produce powders of very
high fineness from dry or wetted feedstock even down to the submicron range. For
wet grinding, the powder is suspended in a liquid upstream milling and then fed in
such form to the mill. Ball mills (Fig. 2.150) are equipped with grinding media. The
bed of balls or grinding beads is put into motion by rotation of the grinding cham-
ber or by an agitator. The feed material is comminuted between the grinding media
because of impact and shear forces. Ball milling can be organized in a continuous
Dust collection
Feed material
Feed material
Grinding balls
Adjustable
discharge slots Finishaed product
Fig. 2.150: A scheme of ball milling [83].

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mode, when the product is pumped to the mill, flows through the agitated bed of
grinding beads and finally exits the mill through a suitable discharge. The volume
of the grinding beads can be approximately 70–80% of the mill volume. The size of
the mills used in catalyst manufacturing is approximately 1–3 m3.
Size enlargement by granulation, which is conceptually similar to a snowball
formation, could be used for large-scale production of support spheres, giving par-
ticles of irregular shape and size. Moreover, particles are less dense and strong com-
pared to tableting and extrusion. During granulation, size enlargement occurs by
wet tumbling-growth agglomeration. Adhesion between wetted particles originates
from capillary forces or can be additionally stabilized by cross-linking if the sprayed
liquid contains binders, which can either undergo hydrolysis and condensation re-
actions or gelation. Better mechanical strength provided by the inorganic binders is
achieved at the expense of the pore size. Alternatively, application of organic bind-
ers necessitates their removal by calcination, leading thereby to lower mechanical
strength.
Granulation can be done by placing the powder, which could be pre-wetted, on
a tilted (45–55° against the floor) rotating pan (Fig. 2.151). The particle growth and
agglomeration occur while the pan is rotating. After reaching a certain size the par-
ticles fall over the rim, which could be higher than 1 m for pans with large diame-
ters of several meters. In addition to growth, several other processes proceed during
granulation, such as wetting and nucleation prior to agglomeration; and also attri-
tion and breakage, which decrease the size of the formed granules. Rotational
speed is adjusted to be 25–40% less than the critical rotation speed at which the
centrifugal force is compensating for the weight. A granulation pan with 3 m diame-
ter tilted to 50° operates between 12 and 15 rpm.
Another method of granulation is to use a cylindrical tilted rotated drum (diam-
eter 0.5–1 m, length up to 3 m) with the granulation mass fed on one side and then
transported through the drum. This mode of operation, where tilting is used solely
for transportation, gives a broader granule size distribution than is obtained with a
granulation pan, requiring downstream granulation.
2.3.7.3 Extrusion
Compared to other preparation methods, the extrusion process affords high
throughput at relatively low costs and gives a variety of possible extrudate shapes.
The downside of the method is a non-uniform shape of extrudates and lower abra-
sion resistance compared to pellets. Moreover, not all catalysts even in the presence
of binders can be shaped by extrusion.
Extrusion of catalysts and supports is different from extrusion of polymers,
when properties of a homogeneous polymer melt can be regulated by the extruder
temperature. Because pastes for catalyst extrusion are highly concentrated disper-
sions, their behavior is determined by rheological characteristics. The pore

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Fig. 2.151: A granulation pan.
structure and mechanical stability of extrudates are determined by the properties of

the paste and extrusion conditions. For catalytic applications, a certain pore struc-
ture is needed to allow transport of the reactants to the active sites. Typically, extru-
dates contain large transport pores of 300–600 nm in addition to mesopores (10–25
nm) being different from materials prepared by tabletting as the latter have mainly
monomodal distribution of mesopores.
During extrusion a wet paste from a hopper at the top is forced through a die, and
the emerging ribbon passing through holes in the die plate is cut to the desired length
using a suitable device. The pressure that is developed in the screw extruder as the
paste moves toward the die is affected by the screw geometry and the paste rheology.
After extrusion, the formed extrudates are either broken because of gravity giv-
ing a non-uniform sized material or cut-off, for example, by a rotating blade. The
cut-off leads to very similar extrudates.
The effect of the extrusion pressure on the compaction in extrusion is, however,
smaller than in pelletizing, because in the former case the particles are suspended
in a liquid. Adjustment of the liquid-to-solid ratio in the extrusion paste is thus

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used not only to influence the apparent viscosity of the paste, which obviously de-
creases when there is more liquid in the paste, but also to vary the porosity of extru-
dates. On the other hand, too high liquid content will prevent the formation of
extrudates after leaving the die. Even if plasticity can be improved by addition of
plasticizers, flow of suspensions is characterized by strong non-Newtonian flow.
While understanding of suspension flow is not yet sufficient to predict extrusion
and control the final properties of catalyst extrudates; nevertheless, rheology is im-
portant in analyzing extrusion processes and will be briefly discussed below.
Flow of suspensions can be described by a single property, namely, the shear
viscosity. Shear is an action of stress when forces are applied causing two contigu-
ous parts of a body to slide relative to each other in a direction parallel to their
plane of contact. Figure 2.152 illustrates deformations produced between parallel
plates when the upper plate of surface area A is moved in response to force F. The
displacement of a plane layer (dx) over the separation between layers (dy) is termed
the shear (dx/dy) acting on the fluid.
Moving plate
Fluid
dx
dy
Stationaty plate
Fig. 2.152: Illustration of deformations between parallel plates.
Depending on the material, there are differences in the behavior when the shear
stress is removed. While a solid will tend to return to its original shape, a plastic
material may show only partial recovery. The force per area in the plane termed the
shear stress (τ) is expressed as
τ = F=A (2:59)
According to the Newton’s law of viscosity, the shear stress is proportional to the
.
derivative dV/dy termed the shear rate γ:

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.
F=A ∝ dV=dy ∝ γ (2:60)
giving dependence of shear stress on shear rate

.
τ=ηγ (2:61)
where η is the coefficient of viscosity having units of mass·length−1·time−1. In SI

.
units, τ is in Pa, γ in s−1; thus, η is expressed in Pa·s. The coefficient of viscosity,
being the ratio of the shear stress to the shear rate, represents the internal resis-
tance to flow of the fluid. Equation (2.61) is applied to Newtonian fluids when vis-
cosity (temperature dependent) does not change with the relative flow velocity. For
the large class of fluids relevant for chemical product technology, this does not
hold and viscosity changes depending on the shear rate
. .
τ = ηðγÞ γ (2:62)
The rheograms for non-Newtonian fluid can often be described by an empirical

power-law function called the Ostwald-de Waele equation
n
dγ
τ=k (2:63)
dt
where k is the consistency index. Materials such as concentrated dispersions used

in preparation of catalysts often exhibit the so-called shear thinning flow, which is
distinctly different from the Newtonian behavior (Fig. 2.153). For shear thinning
(pseudoplastic) n < 1, while for the Newtonian flow n = 1. Shear thickening (dilatant)
fluid has n exceeding unity (n > 1).
Figure 2.153A illustrates a parabolic profile for the Newtonian liquid. Deviations
for shear thinning liquids from the ideal behavior are attributed to a low viscosity
near the wall, where the shear rate is high and a high viscosity in the middle. The
velocity profile is more flat resembling a plug flow. The opposite behavior with a
sharp profile is observed for shear thickening fluids. Dependence of viscosity on the
shear rate is shown in Fig. 2.153B. Shear viscosity decreases or increases with increas-
ing shear rate, leading to, respectively, shear thinning and shear thickening.
The entire flow curve for pseudoplastic behavior can often be fitted using the
Reiner–Philippoff equation:
.
. . η0 − η∞
τ = − γ η∞ + (2:64)
1 + τ2 =A
. .
where A is an adjustable parameter, η0 is viscosity at γ →0, η∞ is viscosity at γ →∞.
An often used model of Herschel–Bulkley is the power-law type of equation
with the addition of a yield stress

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Bingham plastic
Dilatant
Plug flow profile
Shear thinning n<1
Visoosity
Parabolic profile
Newtonian n=1
Newtonian
Sharp profile
Shear thickening n>1
Pseudoplastic
Shear rate
Fig. 2.153: Behavior of suspensions. (A) Flow profiles. Coefficient n appears in eq. (2.63) and
(B) typical curves of viscosity versus shear rate [84].
.
τ = τ0 + kðγÞn (2:65)
.
where τ, τ0 and γ are shear stress, shear yield stress and shear rate; k is the consis-
tency constant and n is the flow index. In this model, viscosity is expressed as
τ0 . n−1
η= . + kjγj (2:66)
jγj
Binders can also influence the flow behavior, altering the velocity profile in the
paste, thereby deteriorating extrudated properties due to inadequate adhesion
during extrusion. The desired product during extrusion (high shear rates) is
achieved for pseudoplastic pastes with low viscosity, since after leaving the die
at a low shear rate the viscosity is increased leading to stable extrudates. Most
catalyst pastes are, however, prone to shear deformation. The flow behavior of
molding masses is well described by Ostwald–de Waele equation (eq. (2.63)).
The flow behavior index n in eq. (2.63) indicates pseudoplastic fluids being for
simple shapes at most 0.7, while for preparation of honeycomb monoliths it is
below 0.3.
Because extrusion of catalysts and supports is in essence defined by the flow of a
suspension inside an extruder, the ability to make an extrudate is determined by the
geometry of the extruder, chemical properties of the screw, wall and die materials,
which should ensure minimal adhesion of the paste, most importantly by the proper-
ties of the paste.
The value of the flow behavior index is related to the velocity profile. There is a
radial profile of flow velocity in the die channel as the flow velocity decreases with
an increasing distance from the flow axis. If the velocity gradient is significant, the
defects will be generated after a granule leaves a die channel because of the

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velocity equalization. Subsequently, efficient molding will not be possible. A small

flow behavior index corresponds to less significant velocity gradients and an ideal
plug flow is achieved when the index is approaching zero.
Molding pastes have non-Newtonian flow behavior and during their movement
through dye channels, different velocity profiles are observed (Fig. 2.154), determin-
ing the tensile strength of shaped catalysts. Obviously, in case of substantial velocity
profiles in the radial direction, produced grains will have macrodefects, originating
from improper “layering” of the material.
Fig. 2.154: Flow deformation profile during extrusion (From [85]).
Pastes that are too viscous can block the extruder, while the opposite leads to un-
stable extrudates. Therefore, an important characteristic of suspensions used in cat-
alyst extrusion is viscosity, which can be expressed by the Einstein equation as a
function of the solid content at low concentrations:
ηr = 1 + 2.5’ (2:67)
where φ is the solid fraction. At higher concentration, the data for relative viscosity
appear to follow more of an exponential function of concentration according to the
Mooney equation:

ξϕ
ηr = exp (2:68)
1 − kϕ
where ζ is a coefficient determined by fitting, constant k is the self-crowding factor,

being in the range between 1.35 and 1.91. The self-crowding factor is inversely pro-
portional to the maximum concentration. The latter has a limit because of the expo-
nential character of the curve. The self-crowding factor at maximum concentration
does not allow the movement of neighboring particles as the suspension acts like a
solid.
Krieger–Dougherty semi-empirical equation describes the concentration depen-
dence of the viscosity:
− K’max
ϕ
ηr = 1 − (2:69)
ϕmax
where φmax is the maximum packing fraction or the volume fraction at which the
zero shear viscosity diverges. Parameter K is equal to 2.5 for spherical particles,

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while deviation from this value is related to shape changes of the particles.
Equation (2.69) reduces to the Einstein relation at low particle concentration.
An alternative approach of Brodnyan–Mooney was developed for ellipsoidal
particles
" #
2.5ϕ + 0.399ðp − 1Þ1.48 ϕ
ηr = ηo exp (2:70)
1 − kϕ
where k is the self-crowding factor.

The treatment above considered suspensions of hard spheres without colloidal or
thermodynamic interactions. Repulsive surface forces stabilize dispersions and pre-
vent aggregation, as the particles are kept away at a certain distance. Electrostatic or
steric repulsion results thus in an excluded volume inaccessible to other particles,
which can be expressed as follows:

a. 3
eff
’eff = ’ (2:71)
a
where aeff is the effective particle radius, which is defined as half the distance to
which centers of two particles can approach each other under colloidal forces.
Rheology of colloids in many cases is similar to hard sphere dispersions being
quantitatively described as a hard sphere system with the concept of effective ra-
dius. Equation (2.71) implies that particle size is a parameter that influences φeff. An
increase in the particle radius a at constant φ and a constant range of the repulsive
colloidal interactions corresponds to a decrease in φeff. This means that dispersions
with the same φ but different a may exist in different phases having a strong impact
on the shear rate-dependent viscosity.
Not only the size but also the particle size distribution can influence the
phase behavior of colloidal dispersions. A significant viscosity decrease is typi-
cally observed by mixing particles with different sizes when the particle volume
fraction φ exceeds 0.5. This effect is more pronounced with increasing φ and the
ratio between large and small particles χ. When repulsive colloidal interactions
become relevant, the viscosity passes through a minimum increasing again
when χ is increased at a constant total particle concentration and a fixed fraction
of small particles.
Attractive particle interactions can lead to large compact aggregates and rapid
phase separation. Alternatively, loose aggregates attract water and increase an ef-
fective volume fraction φeff. This results in an increase in the zero-shear viscosity.
Upon an increase in the shear rate, there is a gradual floc breakdown and/or their
alignment in the flow direction, and as a result a decrease in viscosity.
The extrusion process is influenced by the paste composition: water content
(typically between 20 and 40 wt%); presence of peptizing agents (to adjust the col-
loid-chemical properties of the paste); binders; plasticizers; lubricants and

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porogenes. It is also important that no large solid particles are present for the extru-
sion of complex shapes. The operating variables also include mixing time, aging
and extrusion temperature.
While elevation of temperature is positive, improving relative deformations
from the viewpoint of technology, the process becomes much more energy intensive
and unnecessarily complex. Moreover, temperature fluctuations can influence me-
chanical and rheological properties of the suspension, primarily the optimal water
content. Therefore, extrusion of highly concentrated suspensions is carried out at
ambient temperature.
The paste should be plastic enough to be able to pass through the die and ob-
tain the desired shape. After extrusion, the extrudate should not have any visible or
microdefects having adequate properties for further processing (transport, drying,
calcination, etc.). The coagulation structure of the paste, on the one hand, should
be strong enough ensuring adequate rheological properties and retention of the
shape after leaving the die, and on the other hand, too strong coagulation structure
implies higher energy needed for extrusion.
As already mentioned an important parameter influencing properties of the ex-
trudates is the size of the particles in the suspension, which should be small
enough enhancing plasticity. An energy-intensive operation, ball milling, is typi-
cally applied to reduce the size of the solid phase.
When the amount of water is much lower than the solid pore volume, it might
be difficult to process efficiently such dry pastes. Settling of the pastes after
extruder can be, on the contrary, troublesome for a significant water content
(Fig. 2.155). The amount of water depends on the surface lyophilic and adsorption
properties of the solid phase and its specific surface area. For example, the opti-
mum amount of water in mass% for an alumina support using 20% nitric acid solu-
tion as a peptizing agent is 22–23%, while somewhat higher amount of water
(28–29 mass%) is required when PVA is used instead of nitric acid. A catalyst for
Fig. 2.155: Extrusion of too wet paste (courtesy of Dr. Z. Vajglova).

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oxidation of SO2 to SO3 based on vanadia on silica when processed with sulfuric
acid as a peptizing agent needs as high as 37–38 mass% of water.
Porogenes (carbon black, starch and sawdust) are added to the paste to create
porosity, which is generated during calcination. Besides porogenes, plasticizers and
lubricants are also burned away during calcination, contributing to porosity genera-
tion. Such porosity while beneficial for mass transfer can deteriorate mechanical
stability.
Modification of shaping masses, when the particle sizes are in the (sub)microm-
eter range, from the colloidal viewpoint is controlled by zeta-potential. These sys-
tems that are used in extrusion could be modified, for instance, by the addition of
peptizing agents (e.g., nitric, formic or acetic acids) influencing colloid–chemical
interactions between particles and assuring deviation of pH from the point zero
charge. Otherwise , the liquid phase might start to agglomerate. Corrosivity of pep-
tizing agents (e.g., nitric acid) should be considered when selecting them. In addi-
tion, utilization of nitric acid during extrusion might influence acidity and can give
NOx during calcination. To mitigate these emissions, a selective catalytic reduction
of NOx should be installed, obviously increasing the catalyst production costs. As a
consequence, application of electrolytes as peptizing agents is justified when other
methods to regulate rheological properties of suspension pastes are not successful.
Plasticizers or their mixtures applied to improve the paste rheological behavior
are selected from a wide variety of plasticizers, including clays, starch, sugars, cel-
lulose derivatives, polyethylene glycol and PVA. The amount of plasticizers should
not be too high (up to 3–5 mass%), corresponding to covering the available surface
of the solid and allowing the desired changes in rheological properties. Higher con-
centration might not be beneficial from the rheological viewpoint. Selection of rhe-
ology improvers should also consider potential adhesion of the suspension paste to
the extruder material, which should be minimized.
Formation of shaped catalysts implies cross-linking between particles in the
suspension, which can be achieved either by condensation of surface hydroxyls, re-
sulting in oxygen bridges, or by sintering. In the absence of suitable surface hy-
droxyl groups in many catalysts or catalyst precursors, addition of inorganic
binders allows interparticle cross-linking. Binders, such as hydroxide forms of alu-
mina, silica–alumina, clays or silica sols applied together with the catalytic phase
result in cross-linking at sufficiently low temperatures avoiding thereby damage of
the catalytically active material. Binders required during extrusion make the extru-
dates strong enough, preventing a potential collapse.
Typically, inorganic binders are utilized because organic ones will be burned
away at the calcination step at 500–600 °C, which also results in the burnout of
organic additives like plasticizers.
In many cases, the catalytic pastes cannot be shaped without adding binders.
When alumina is added in the form of boehmite or pseudoboehmite, it is trans-
formed into transition alumina during calcination. Gelation of silica sols and

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agglomeration of delaminated fragments of clays are responsible for the stability of

extrudates when these binders are used.
Introduction of binders can influence catalytic activity sometimes in a negative
way. In such a case, a compromise should be made between the rheological proper-
ties and mechanical stability on one hand, and catalytic behavior, on the other. For
example, introduction of aluminosilicates for extrusion of monolithic blocks based
on titania improves the rheological properties of the suspension paste at the ex-
pense of the catalytic properties.
A special care should be taken on the surface properties of binders, which can
be themselves catalytically active. In production of traditional ceramics, this is a
rare case. In production of catalysts by extrusion, there are, however, several ex-
amples when the main active component and the binder influence each other,
which has a consequence in terms of physicochemical properties of the final cata-
lyst. Figure 2.156 shows temperature-programmed desorption of ammonia from
fresh forms of H-ZSM-5 zeolite and the material with aluminum phosphate as a
AlPO binder.
Pure zeolite powder

Phosphate-bound zeolite
NH3 des. (a.u.)
0 100 200 300 400 500

Temperature/ oC
Figure 2.156: Ammonia TPD of H-ZSM-5 powder after calcination and AlPO4-bound extrudate
containing the same zeolite. Reproduced with permission from [86].
There are evident changes in acidity after addition of a binder resulting in another
distribution of sites in terms of acidic strength. Such an example of the binder influ-
ences on the acidic strength, and thus catalytic properties can be interpreted by the
phosphor migration from the binder to the zeolite crystal structure.
Application of binders can result in nonuniformity of the active component dis-
tribution. It implies that there could be zones with a high concentration of the

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active phase, and consequently, higher rate, maybe local overheating and appear-
ance of zones which are controlled by mass transfer rather than kinetics.
Special shapes (trilobates, rings, hollow cylinders, monoliths or honeycombs)
can be obtained using proper dies (Fig. 2.157).
Fig. 2.157: Shapes of extruded catalysts.
Internal cavities can be formed when, for instance, a two-piece aluminum extrusion
die set is used. In a set with separated parts, the piece at the right of Fig. 2.158 is
used for forming the internal cavity.
Fig. 2.158: A two-piece aluminum extrusion die set to form extrudates with an internal cavity [87].
The quality of the extrudates depends not only on extrusion but also on down-
stream drying and calcination. These steps require special attention in the case of
larger structures such as extruded monoliths, which are applied in SCR of NOx at
power and waste incineration plants or the destruction of dioxins generated during
incinerating municipal wastes. The active phase V2O5 is deposited on titania (ana-
tase) support. To improve the mechanical strength, silicoaluminates or glass fibers
are added as mechanical promoters (3.5 wt%). The suspension for extrusion con-
tains clays (ca 6.5 wt%), water and small amounts of methyl hydroxyethyl cellulose
and polyethylene glycol as lubricants. Drying of the extruded monolith must be
slow enough to prevent ruptures and cracks. Calcination is performed at approxi-
mately 500 ± 600 °C.

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Screw extruders with short screw length to barrel diameter are used for cata-
lysts requiring less viscous pastes. For more viscous pastes, press extruders with a
rotating pressing cylinder are utilized due to shorter distance at which the pressing
force is applied. Figure 2.159 shows that this distance is just between two cylinders,
the pressing and the screening ones. Because of lower shear deformation, the flow
behavior of the paste is less critical than in screw extruders. The latter allow, how-
ever, production of extrudates with more complex shapes.
Pressing
cylinder
Screening cylinder Fig. 2.159: Extruder press.
As an example of mechanical mixing and extrusion during catalyst preparation, the

synthesis of sulfuric acid catalyst of the SVD type (on diatomite) is illustrated in
Fig. 2.160.
Diatomite
2
KHSO4 K2SO4
H2SO4
5
Hot air 7
V2O5 3 9
Plasticizer
4
Flue gases
10
Fig. 2.160: Production of sulfuric acid catalyst. (Redrawn from [48].) 1, dryer; 2, bunker; 3, grinder;
4, vibration milling; 5, ball milling; 6, extruder; 7, reactor for potassium bisulfate; 8, dryer; 9,
calcination; 10, sieve.

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The active component in this catalyst is vanadium pentoxide promoted with

sulfates of alkali metals, potassium and sodium. The support is diatomite, which is
silica with some minor presence of other oxides such as Fe2O3 and Al2O3. The cata-
lyst performance depends very much on the type of diatomite.
The support is dried in a spray dryer at 120–150 °C up to a humidity of 5–7%. The
technical quality vanadium pentoxide (80% of V2O5) is ground up, first to 2–3 mm
(pos. 3) and then to ~200 μm (pos. 4). After mixing and ball milling (pos. 5) the solid
phase, containing diatomite and vanadium pentoxide, is extruded with the addition
of potassium hydrosulfate (promoter), stearic acid (plasticizer) and graphite (poro-
genes) directly to the extruder. Potassium bisulfate is prepared in the reactor (pos. 7)
by contacting potassium sulfate with sulfuric acid. The extrudates contain 26–30%
water and are thus dried at 120 °C (pos. 8) and calcined (pos. 9). During calcination
the following reactions occur
2KHSO4 = K2 S2 O7 + H2 O; K2 S2 O7 + V2 O5 = K2 S2 O7 · V2 O5
In this example the supported catalyst was produced by a dry method of mechani-
cal mixing with subsequent calcination. This procedure leads to a catalyst when va-
nadium is present as a complex sulfated salt mixture, which is in the molten state
during actual catalysis.
2.3.7.4 Tableting
Pellets or tablets of high shape accuracy, much better than in extrusion, are ob-
tained by dry tableting when a dry powder is pressed between two punches in a
press. The powder flows through a feeder mechanism, and is filled into a rotating
die, where it is compressed by pistons (Fig. 2.161). The maximum pressure and the
rate of the pressure are the parameters influencing pellet hardness and integrity.
High mechanical stress during tableting has the downside of potential crushing of
crystals, dislocations of crystal planes and low porosity, typically not exceeding
Fig. 2.161: A tableting machine cycle.

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30%, thereby the formulation can contain porosity improvers if porosity is impor-
tant for the final application.
At the start of the cycle, the lower piston is in the upper position. The pellet
made in the previous cycle is pushed out as the die passes under the feeder mecha-
nism. The upper piston moves down by a fixed length, which defines the dimension
of the pellet. Although usually simple cylinders with almost the same height and
diameter are produced, it is also possible to form ring-shape tablets with special
dies and punches.
The important parameter in tableting is plastic deformation, which depends on
the applied stress, overall time and rate of compression, and the time for the mate-
rial to be under maximum stress. The elastic component of the response to the ap-
plied pressure stored in the material is relaxed after the pressure release. A too high
elastic component gives unstable tablets.
Small amounts of liquid or solid additives may be used to prevent dust formation
and improve compaction by lubrication. Because in tableting dry feeds are used, thus
lubricants or pilling aids such graphite, PVA, polyethylene, talc, silicates, alumi-
nates, to name a few, are added to enable the powder to flow. One of the most fre-
quently used additives is graphite at concentrations between 0.5 and 1%. If for some
reasons application of graphite can deteriorate catalyst performance, it should be re-
moved by careful oxidation.
In general, the feed for tableting should have flow properties of sand. Mechanical
stability after compression can be improved by adding binders. Moreover, high me-
chanical stability is obtained when the feed consists of mixed particle sizes. If the feed
is not sufficiently dense prior to tableting, pre-compacting is applied.
Different geometries can be achieved during tabletting including tablets per se
when the height is low than the diameter or cylinders when the opposite holds
(height > diameter). Moreover, cylinders with holes or ribs on the external surface
as well as their combination can be manufactured.
An example of nickel-molybdenum alumina catalyst preparation is shown in
Fig. 2.162. Suspension of aluminum hydroxide and water solutions of NH4MoO4 and
nitric acid are prepared respectively in vessels (pos. 1–3) and then mixed in a reac-
tor (pos. 4). Thereafter the tablets are produced from this mixture (pos. 6). After dry-
ing at room temperature (pos. 7) for 24 h the tablets are first dried at 383–423 K for
12 h and then calcined at 803 K for 8 h. After grinding the tablets to the powder
size, the powder is impregnated with Ni(NO3)2 for 1 h in the reactor (pos. 4).
Subsequent tableting, drying and calcination give the final catalyst that contains
13–15 wt% MoO3, 3–4 wt% NiO, 0.05–0.1 wt% Na2O, 0.2–0.3 wt% Fe2O3 and alu-
mina (the rest). Approximately 30 kg of NOx is released per ton of catalyst.

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(NH4)MoO4
Al(OH)3 H2O H2O HNO3 H2O
Ni(NO3)2
1 2 3 5 NaOH
12
Steam
13 14
8
4 9
6 7
Gas 11
10
Air
Air
Fig. 2.162: Production of nickel-molybdenum alumina catalyst. (From [48].) 1, 2, 3, 5, vessels for
Al(OH)3 suspension and water solutions of NH4MoO4, HNO3, Ni(NO3)2; 4, reactor; 6, tableting
machine; 7, oven; 8, lift; 9, calcination unit; 10, burner for flue gases generation; 11, heat
exchanger; 12, absorber with caustic solution; 13, milling; 14, intermediate vessel.
2.3.7.5 3D printing in catalytic technology

The 3D printing process is a promising manufacturing method, which can in the fu-
ture be applied to many different catalytic materials, allowing careful design of tar-
geted structures. The method is suitable for large-scale manufacturing as well as for
catalyst development being applicable to lab-scale operations. 3D printing allows ac-
curate control of various sophisticated structures, including monolithic catalysts with
a complex preparation procedure. Not surprisingly, additive manufacturing tools
(e.g., 3D printing) have been mainly explored for shaping 3D catalyst bodies such as
structured monoliths with improved mass and heat transfer characteristics.
Figure 2.163 illustrates a comparison between an extruded monolith and a robocast
structure with FCC (Fig. 2.163C) lattice. In robocasting, highly concentrated suspen-
sions of the material and a solvent are deposited in a layer-wise fashion through a
syringe-type nozzle. The minimum printable feature size in robocasting is typically
30–500 μm.
Besides fabricating structured monoliths, geometrically complex reaction vessels
and microreactors with integrated catalysts can be manufactured using 3D printing,

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20 mm
(a) (b) (c)
Fig. 2.163: Monoliths of similar outer dimensions and surface areas: (a) extruded honeycomb, (b)
robocast material with (c) FCC lattice (Reproduced from [88]).
when the structure of the target material can be first designed through computer-
aided design.
The most suitable methods for catalyst preparation include (Fig. 2.164) fused
deposition modeling (FDM), direct ink writing (DIW), stereolithography (SLA) and
selective laser sintering (SLS).
In SLS a laser is used as the power source to sinter a powdered material, while
in SLA layer-by-layer deposition is done using photochemical processes. DIW (robo-
casting) is an extrusion-based printing process similar to FDM with the difference
that contrary to the latter process in DIW, the material is extruded directly without
melting or solidification.
Similar to extrusion processes described earlier, a low viscosity of the printing
ink is required for maintaining fluidity while passing through the nozzle. Thereafter,
the material should maintain the shape on the printing structure, which implies high
viscosity. Pseudoplastic fluids used in robocasting typically require utilization of a
solvent, necessitating post treatment drying and sintering. In addition to solvents,
mixtures for robocasting of more complex materials, such as zeolites, should contain
different additives aiding extrusion (e.g., clays and plasticizing organic binders).
Future advances in 3D printing of catalysts require [89]:
– better control of the micro/mesostructures of printed catalytic materials by im-
proving the accuracy;
– improvement of the feedstock materials to diminish processing costs;
– structural optimization of 3D-printed materials, including pore size, pore struc-
ture and active phase distribution;
– better preservation of the 3D-printed structures after post-treatment processes.

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(a) Fused deposition modeling (b) Stereolithography
Lenses
Material filament
Scanning mirror
Step motor Laser
Liquifier Build platform Part Elevator
Extrusion nozzle
Part Sweeper
Vat
Build platform
Liquid photopolymer
Material spool
(c) Direct ink writing (d) Selective laser Sintering
Lenses
Scanning mirror
Extruder
Laser
Powder supply
Extrusion nozzle Powder bed Part
Part
Leveling roller
Build platform
Build piston
Figure 2.164: Some 3D printing processes that are useful for catalyst preparation: (a) fused
deposition modeling; (b) stereolithography; (c) direct ink writing; and (d) selective laser sintering.
(From [89]).
2.3.7.6 Scaling-up catalyst preparation

The typical strategy in academic work on catalyst design is related to the use of cat-
alyst particles of such a size that diffusion limitations are suppressed. Of less con-
cern are the preparation methods and selection of precursors, which are feasible for
use on an industrial scale. For example, metal chlorides could be used for impreg-
nation on a laboratory scale, while nitrates are preferred industrially. Catalyst re-
duction in academia is usually carried out by molecular hydrogen, while some
catalyst manufactures prefer reduction with chemical reagents. There is therefore a
difference in catalytic materials prepared on a small scale and those used for pilot-
ing and eventual production. For example, the type of the support or the

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preparation method should not necessarily be the same. Commercial raw materials
are used for catalyst preparation in a large scale instead of pure chemicals on a lab-
oratory scale. Water is the most used solvent, while the use of organic solvents is
uncommon.
In lab scale, costs of chemicals are rarely considered, while cost-effective raw
materials should be selected for industrial production. Moreover, the corrosive na-
ture of raw materials, possibility of emissions and their mitigation, efficient dis-
posal of effluents, wastewater purification along with process water recovery
should be carefully considered, limiting catalyst preparation technology. Low slurry
concentration during precipitation can be, for example, applicable in lab-scale rec-
ipes but will be challenging from the production technology viewpoint.
Preparation of catalysts for larger than lab scale is not straightforward as pa-
rameters such as stirring rate, heating and cooling rates, heat transfer, flow pattern,
drying and calcination conditions can be different. In particular, heating and cool-
ing rates are much slower when the scale is increasing. This influences chemical
and physical process in catalyst preparation, for instance, crystallization by hydro-
thermal synthesis.
In addition, large reactors have more prominent spatial inhomogeneity in tem-
perature, pH and concentration. As the size increases, significant variations in the
local temperature profiles are possible during drying and calcination. Proper equip-
ment design is thus essential to minimize different spatial variations. Larger pro-
duction volume also requires equipment capable of handling such volumes.
Preparation methods used in industry are mainly kept as trade secrets or cover
a broad range of parameters, making it difficult to reveal the exact preparations de-
tails. Very few flow schemes for catalyst preparations can be found in the open
literature.
In general, scaling up the catalyst preparation procedure is not an easy task. In
pilot scale and industrial fixed-bed reactors, usually larger catalyst particles are
used than in the laboratory scale where the aim is to avoid problems with the pres-
sure drop. This can result in changes not only in the reactant conversion but also in
the product selectivity, which is known to be influenced by internal and external
diffusion.
Lab-scale academic research, aimed primarily at publications in high-impact
factor journals, does not typically consider a necessity of a high crush strength re-
quired for applications in fixed bed reactors, when also a minimally allowed pres-
sure drop should be achieved. This requirement implies higher compaction during
forming at the expense of porosity as well as elevated heat and mass transfer within
the catalyst particle. The latter can obviously influence activity and selectivity. Not
only the value of the crushing strength is of importance, but also the distribution in
strength, in particular percentage of catalyst particles with low strength should be
minimal, as otherwise the particles will break giving high pressure drop.

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Another important issue is the presence of a binder, for example, for extrusion.
Introduction of a binder can influence the catalyst performance, thus such differen-
ces should be recognized when progressing from laboratory to pilot and industrial
scale with kinetic and diffusion modeling.
Catalyst stability is an important issue that is often not in the focus of experi-
mental and theoretical studies at the laboratory scale. The necessity to develop ma-
terials and structures resistant to deactivation also requires some alterations on the
material level, resulting in a difference between catalysts tested in a lab and on an
industrial scale. In conclusion the scale-up of the catalyst preparation methods
from a laboratory scale to pilot and industrial scales is challenging, which calls for
more widespread involvement of the theories of physical chemistry and chemical
engineering in catalyst preparation.
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2 Engineering catalysts

2.1 Catalyst design

Heterogeneous catalysts, as discussed in Chapter 1, are nanomaterials and thus

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Micropores Mesopores Macropores

Activated carbon, Mesoporous materials Ceramics

Fig. 2.2: Classification of pores.

Finally, for the understanding of the events occurring at macroscopic or reactor

2.1.1 Being in shape

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Fig. 2.3: Pressure drop in fixed-bed reactors. Courtesy of Dr. E. Toukoniitty.

Sphere Cloverleaf extrudate Irregular granule

Ring extrudate Pellet Cylinder extrudate

Trilobe Metal gauze Monolith

Fig. 2.4: Various catalyst shapes.

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Uniform Egg-shell Egg-white Egg-yolk

Fig. 2.5: Various concentration profiles in catalyst particles: active phase.

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Fig. 2.7: Geometry of channels in monoliths.

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(A) (B) Sampling valve

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Spinning disks reactor

Light reactant Heavy reactant

Fig. 2.10: Spinning disk reactor. (From [3]).

Fig. 2.11: Polyethylene fiber catalyst.

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2.1.2 Catalysis informatics and high-throughput experimentation

In the recent years, catalysis informatics and high-throughput experimentation

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Synthesis Methods from inorganic chemistry, Methods similar to industrial preparation,

Testing Fast testing, conditions different from Lab reactors, considerations of

Analytics Dedicated, qualitative and Quantitative (conversion, selectivity),

Application Discovery of novel materials Improvement of known systems,

Conventional fixed-bed microreactors with complete analysis of reactants and prod-

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2.2 Toolbox in catalysis

2.2.1 General overview of the characterization methods

Catalyst characterization is required for understanding relationships among physi-

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Machine-learned Catalyst synthesis

Catalyst structure Catalyst prediction

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Fig. 2.14: Input–output structures of some analytical methods.

In electron microscopy the overall contrast is caused by the different adsorption of

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inductive coupled plasma-MS (ICP-MS, when a sample solution is introduced into

2.2.2 Adsorption methods

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2.2.3 Physisorption methods

Low-temperature adsorption at a gas condensation temperature (i.e., for nitrogen

2.2.3.1 Surface area determination

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(A) (B) Adsorbate Adsorbent

Fig. 2.16: IUPAC classification of isotherms.

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Type H1 Type H2 Type H3 Type H4

Tab. 2.2: Values of the areas occupied by typical adsorbates.

Adsorbate Boiling point (K) Am (nm/molecule)

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Fig. 2.18: Schematics of desorbed layers.